Active components and photosensitive resin composition containing the same

ABSTRACT

A photosensitive resin composition for using in combination with a photosensitizer comprises an active component selected from an active metal alkoxide represented by the formula (1) or a polycondensate thereof and a particle represented by the formula (2),  
     (X) m−n -M m -[(U 1 ) p -(U 2 -Z) t ] n   (1)  
     P—[(Y) s -{(U 1)   p -(U 2 -Z) t }] k   (2)  
     wherein, X shows a hydrogen, a halogen, an alkoxy group or an alkoxycarbonyl group, M shows a metal atom whose valence m is not less than 2, U 1  shows a first connecting unit, U 2  shows a second connecting unit and Z shows a group causing a difference insolubility by light exposure, P shows a fine particle carrier, Y shows a coupling residue, n shows an integer of not less than 1 and m&gt;n, p shows 0 or 1, t shows 1 or 2, k shows an integer of not less than 1, and s shows 0 or 1).  
     The unit (U 1 ) p -(U 2 -Z) t  is represented by the following formula: [(R 1 ) q —(B) r ] p —[{(R 2 ) u —(Ar) v }-Z] t    
     (wherein, R 1  and R 2  show an alkylene or alkenylene group; and B shows an ester bond, an amide bond, a urea bond, a urethane bond, an imino group, a sulfur atom or a nitrogen atom; Ar represents an arylene or cycloalkylene group; each of the factors, q, r, u and v, shows 0 or 1, and q+r+u+v≧1; and Z, p and t have the same meanings defined above).

TECHNICAL FIELD

[0001] The present invention relates to an active component which isuseful for forming minute patterns such as semiconductor integratedcircuits using a beam, for example, ultraviolet rays or far-ultravioletrays (including excimer lasers or the like); a photosensitive resincomposition (resist composition) using the same; and a process forforming a pattern using the same.

BACKGROUND ART

[0002] In the field of semiconductor resists, with developing very largescale integrated circuits, higher minute processing techniques have beendemanded. Thereupon, light sources of shorter wavelength such as KrFexcimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193nm) and F2 excimer laser (wavelength: 157 nm) are utilized instead ofg-ray (wavelength: 436 mm) or i-ray (wavelength: 365 mm) of aconventional high-pressure mercury lamp.

[0003] However, even when KrF excimer laser or ArF excimer laser isapplied to a conventional resist material such as a novolakresin/diazonaphthoquinone-based positive resist, in which g-ray or i-rayis used, sensitivity and resolution of the conventional resist materialsare considerably deteriorated owing to light absorption by the novolakresin.

[0004] Moreover, with rises in the integration level and performance ofsemiconductor integrated circuits, there has been demand for resistswith better resolution (patterns in submicron order, quartermicron orderor smaller) and for improvement of etching resistance in the process ofdry development.

[0005] For example, as an approach for improving resolution with the useof conventional process for dry development, there has been known amethod in which a photosensitive resin is filled with inorganic fineparticles, and silicasol and the like are utilized as the inorganic fineparticle to impart both resist performance (sensitivity, resolution,etc.) and dry etching resistance. To illustrate, in order to improve dryetching resistance, Japanese Patent Application Laid-Open No.158235/1993 (JP-5-158235A) discloses a resist composition comprising aresist composed of a cresol novolak resin and naphthoquinonediazidosulfonic ester, in which silicasol added to the resist, and the resistcomposition is used as an upper layer resist of bilayer. Japanese PatentApplication Laid-Open No. 194491/1999 (JP-11-194491A) proposes aphotosensitive resin composition, which comprises a photosensitiveorganic oligomer or polymer, a hydrolyzable and polymerizable organicmetal compound or its condensate, and an inorganic filler having afunctional group (e.g., silicasol). Japanese Patent ApplicationLaid-Open No. 327125/1999 (JP-11-327125A) discloses a photosensitiveresin composition comprising a photosensitive resin, an inorganic fineparticle (e.g., silicasol) or an inorganic fine particle having afunctional group. Sondi and Matijevic disclose a film composed of ap-hydroxystyrene-t-butyl acrylate copolymer containing SiO₂nanoparticles (silicasol), and report that the SiO₂ nanoparticle ishighly soluble in a base to act as a solution accelerator and that theresist including such a SiO₂ nanoparticle shows almost the sameresolution with control (resist) not comprising SiO₂ (I. Sondi and E.Matijevic, Resist Technology and Processing XVII, Francis M. Houlihan,Editor, Proceedings of SPIE Vol. 3999(2000), pp. 627-637). Moreover,this literature discloses that a resist system using a transparent SiO₂nanoparticle is useful to wavelengths such as 157 nm.

[0006] On the other hand, with the improvement of miniaturization,recently, edge roughness of resist patterns has been becoming of aproblem in particular. The edge roughness is particularly prominent inthe resist used in thin films such as surface layer resists.

[0007] In the above-mentioned resist comprising a silicasol addedthereto, a film can be thickened because the silicasol is small in aparticle size and is transparent to exposure beam. Further, owing to thesmall size of silicasol particle, thin film is also obtainable andresolution thereof can be improved to a certain degree. However, sincethe resist is dissolved at the area where the resist is inhibited fromdissolution (e.g., non-exposed area in the case of positive resist) dueto high hydrophilicity of silicasol itself, difference in dissolutionrate between exposed area and non-exposed area cannot be increased(enlarged) in the above-mentioned resist, therefore resolution, andsharpness or edge roughness of pattern profile cannot be greatlyimproved.

[0008] Moreover, a commercially available silicasol is mostlymanufactured by sodium silicate method, therefore sodium may beinevitably left in the products.

[0009] Japanese Patent Application Laid-Open No. 56463/2000(JP-2000-56463A) discloses that an alcohol solution of a resist materialcontaining an alkali-soluble resin is added with an organooxysilane, andsubjected to a sol-gel reaction in the presence of moisture to give asilica-alkali soluble resin hybrid material. In this method, a silicacomponent can be uniformly dispersed in the resist material on molecularlevel with the silica components prevented from precipitation, byconducting a sol-gel reaction in the resist. However, great improvementof resist performance such as resolution is hardly achieved by thismethod because the difference in solubility between exposed area andnon-exposed area in a developer cannot be enlarged.

[0010] Moreover, as a resist composition, there has been known alight-amplifying (chemical-amplifying) resist composition comprising abase resin which becomes alkali-soluble with leaving (removing) by anaction of an acid, in combination with a photoactive acid generator.However, the difference in solubility between exposed area andnon-exposed area cannot be increased even in this composition.

[0011] Accordingly, it is an object of the present invention to providean active component (including an active particle), that is useful forforming a pattern with high sensitivity and high resolution; aphotosensitive resin composition comprising the active component; and aprocess for forming a pattern using the photosensitive resincomposition.

[0012] It is another object of the present invention to provide aphotosensitive resin composition which improves edge roughness of thepattern with etching resistance against oxygen plasma kept; and aprocess for forming a pattern.

[0013] It is still another object of the present invention to provide aphotosensitive resin composition which is efficient for largelyimproving resolution with high sensitivity to shorter wavelength beams(rays); and a process for forming a pattern using the same.

[0014] It is other object of the present invention to provide an activecomponent (including an active particle) useful for forming a patternwith high sensitivity and high resolution in which contamination ofimpurities is inhibited (avoided); an active metal alkoxide useful forproviding the active component; a photosensitive resin compositioncomprising the active component; and a process for forming a patternusing the photosensitive resin composition.

[0015] It is still other object of the present invention to provide aphotosensitive resin composition and a process for forming a patternusing the same, which can cause (make) a difference in solubilitybetween exposed area and non-exposed area in a developer.

DISCLOSURE OF INVENTION

[0016] The inventors of the present invention made intensive andextensive studies to achieve the above-mentioned objects and finallyfound that the combination use of an active component and aphotosensitive resin composition is attributed to forming highresolution pattern with high sensitivity because of a difference insolubility in a developer between exposed area and non-exposed area,wherein a functional group is introduced into the active component[e.g., a fine or finely divided particle (an active particle) capable ofbeing hydrophilic by eliminating a hydrophobic leaving group owing to atleast light exposure, a specific metal alkoxide (an active metalalkoxide) or the polycondensate thereof (an active particle formed bypolycondensation)] to cause (yield) a difference in solubility owing tolight exposure, and that the combination use of the metal alkoxide or apolycondensate thereof, and a photosensitive resin composition, isattributed to forming high(er) resolution pattern with highersensitivity because of reduction of impurity incorporation. The presentinvention was accomplished based on the above findings.

[0017] That is, the active component (constituent) of the presentinvention is the one for using (the one which is used or usable) incombination with a photosensitizer which constitutes a photosensitiveresin composition, wherein the component comprises at least one memberselected from the group consisting of an active metal alkoxiderepresented by the following formula (1):

(X)_(m−n)-M^(m)-[(U₁)_(p)-(U₂-Z)_(t)]_(n)  (1)

[0018] (wherein, X represents a hydrogen atom, a halogen atom, an alkoxygroup or an alkoxycarbonyl group, M represents a metal atom whosevalence m is not less than 2, U₁ represents a first connecting unit, U₂represents a second connecting unit, Z represents a group causing(making) a difference in solubility by (through or owing to) lightexposure, n represents an integer of not less than 1 and m>n, prepresents 0 or 1, and t represents an integer of not less than 1 (e.g.,1 or 2)), or a polycondensate thereof, and a particle (particulate)represented by the following formula (2):

P—[(Y)_(s)-{(U₁)_(p)-(U₂-Z)_(t)}]_(k)  (2)

[0019] (wherein, P represents a fine (minute) particle carrier, Yrepresents a coupling residue, k represents an integer of not less than1, s represents 0 or 1, and U₁, U₂, Z, p and t have the same meaningsdefined above). Incidentally, the first connecting unit U₁ and thesecond connecting unit U₂ are generically referred to as connecting unitU in some cases. The particle (active particle) represented by theformula (2) may be a reaction product of an active metal alkoxiderepresented by the formula (1) or a polycondensate thereof, with a fineparticle carrier P.

[0020] The active component may be in the form (morphology orconfiguration) of a particle or an oligomer, and the group Z may be (a)a photo-crosslinkable group or a photo-curable group, or (b) ahydrophilic group protected by a protective group which is capable(competent or qualified) of removing (removable) by (owing to) lightexposure. The group Z may be usually a hydrophilic group protected by aprotective group which is capable of removing (removable) by lightexposure in association with a photosensitizer, and the protective groupis capable of removing (removable) by an action of an acid and others.The group Z is capable (competent or qualified) of forming (formable orform-able) a hydroxyl group or a carboxyl group by removal (elimination)of a hydrophobic protective group, and such a group Z is represented,for example, by a group —HP-Pro (wherein, HP represents a hydrophilicgroup and Pro represents a protective group which imparts hydrophobicityto the hydrophilic group HP and forms the hydrophilic group HP byremoving (leaving) owing to light exposure).

[0021] The protective group may be (i) a protective group for a hydroxylgroup, selected from the group consisting of an alkoxyalkyl group, anacyl group, an alkoxycarbonyl group, an oxacycloalkyl group and acrosslinked cyclic alicyclic group; or (ii) a protective group for acarboxyl group, selected from the group consisting of an alkyl group, acarbamoyl group and a crosslinked cyclic alicyclic group. Specifically,the protective group may be (1) a protective group for a hydroxyl group,selected from the group consisting of a C₁₋₆alkyl-carbonyl group, aC₁₋₆alkoxy-C₁₋₆alkyl group, a C₁₋alkoxy-carbonyl group and anoxacycloalkyl group; or (2) a protective group for a carboxyl group,selected from the group consisting of a C₁₋₆alkyl group, a carbamoylgroup, a C₁₋₆alkyl-carbamoyl group, a C₆₋₁₀aryl-carbamoyl group and abi- or tricycloalkyl group.

[0022] The metal atom M may be aluminium, titanium, zirconium orsilicon, is usually silicon.

[0023] The connecting units U₁ and U₂ may comprise various connectinggroup, for example, may comprise a unit containing at least one memberselected from the group consisting of a chain hydrocarbon, a hydrocarbonring, a chain hydrocarbon having a hetero atom, and a heterocycle. Forexample, the connecting units U₁ and U₂ may be respectively representedby the following formulae:

—(R¹)_(q)—(B)_(r)—, —(R²)_(u)—(Ar)_(v)—

[0024] (wherein, each of the factors, R¹ and R², is either same ordifferent, representing an alkylene group or an alkenylene group, Brepresents an ester bond, a thioester bond, an amide bond, a urea bond,a urethane bond, a thiourethane bond, an imino group, a sulfur atom or anitrogen atom, Ar represents an arylene or cycloalkylene group which mayhave a substituent (e.g., a halogen atom and an alkyl group), each ofthe factors, q, r, u and v, represents 0 or 1, and q+r+u+v≧1).

[0025] The compound represented by the formula (1) may be a one in whichZ means a hydroxyl or carboxyl group protected by a hydrophobicprotective group which is capable of removing (removable) by (owing to)light exposure, the metal atom M is selected from the group consistingof aluminium, titanium, zirconium and silicon, and the unit(U₁)_(p)-(U₂-Z)_(t) containing a connecting unit is represented by thefollowing formula:

[(R¹)_(q)—(B)_(r)]_(p)—[{(R²)_(u)—(Ar)_(v)}-Z]_(t)

[0026] (wherein, R¹, R², B, Ar, p, q, r, t, u and v have the samemeanings defined above).

[0027] Further, the polycondensate of the active metal alkoxide (1) maybe a polycondensate of the active metal alkoxide represented by theformula (1) alone (singly) or a polycondensate (copolycondensate) of theactive metal alkoxide represented by the formula (1) and a metalalkoxide represented by the following formula (5):

(X)_(m−n−1)M^(m)(R⁵)_(n−1)  (5)

[0028] (wherein, R⁵ represents a hydrogen atom or an alkyl group, X, M,m and n have the same meanings defined above).

[0029] The weight ratio of the active metal alkoxide (1) relative to themetal alkoxide (5) may be, for example, about 10/90 to 90/10. Thepolycondensate may be in the form of a particle (particulate), forexample, a particle having a mean particle size of about 1 to 100 nm.

[0030] In the particle (active particle) represented by the formula (2),the mean particle size of the fine particle carrier may be about 1 to100 nm. The fine particle carrier may be an organic fine particlecarrier or an inorganic fine particle carrier (e.g., silicasol).Incidentally, a coupling agent associates with a compound having themetal atom M of the formula (1). Such an active particle (2) maycomprise a connecting unit U connecting with an inorganic fine particleP whose mean particle size is 1 to 50 nm through (via) a silane couplingagent Y, a hydrophilic group connecting with the connecting unit, and aprotective group which protects the hydrophilic group. Moreover, thegroup Z which causes (makes) a difference in solubility by (through)light exposure may comprise the hydrophilic group and the protectivegroup. The connecting unit may comprise at least one member selectedfrom the group consisting an aromatic C₆₋₁₂hydrocarbon ring, amonocyclic alicyclic hydrocarbon ring, a crosslinked cyclic alicyclichydrocarbon ring and an aliphatic hydrocarbon chain, and the hydrophilicgroup is usually a hydroxyl group or a carboxyl group. The protectivegroup may be (1) a protective group for the hydroxyl group, selectedfrom the group consisting of a C₁₋₄alkyl-carbonyl group, aC₁₋₄alkoxy-C₁₋₄alkyl group, a C₁₋₄alkoxy-carbonyl group and a 5- or6-membered oxacycloalkyl group, or (2) a protective group for thecarboxyl group, selected from the group consisting of a C₁₋₄alkyl group,a carbamoyl group, a C₁₋₄alkyl-carbamoyl group, a C₆₋₁₀aryl-carbamoylgroup and a bi- or tricycloalkyl group. The amount of the silanecoupling agent may be about 0.1 to 200 parts by weight relative to 100parts by weight of the fine particle carrier.

[0031] The present invention includes a photosensitive resin compositioncontaining the active component, for example includes a photosensitiveresin composition which comprises a base resin, a photosensitizer andthe active component. The photosensitive resin composition may be apositive one in which an exposed area is water- or alkali-soluble. Forexample, the photosensitive resin composition may be a one in which abase resin comprises a homo- or copolymer of a monomer which is capableof forming (formable) a hydrophilic group by an action of an acid, and aphotosensitizer comprises an photoactive acid generator. In order toform a pattern, such a photosensitive composition may be applied orcoated onto a substrate, the coating layer may be exposed to light, thelight-exposed layer may be heat-treated, and the heat-treated layer maybe developed.

[0032] The present invention includes an active metal alkoxide which isrepresented by the following formula (1):

(X)_(m−n)-M^(m)-{(U₁)_(p)-(U₂-Z)_(t)}_(n)  (1)

[0033] (wherein, X represents a hydrogen atom, a halogen atom, an alkoxygroup or an alkoxycarbonyl group, M represents a metal atom whosevalence m is not less than 2, U₁ represents a first connecting unit, U₂represents a second connecting unit, Z represents a group causing adifference in solubility by light exposure, n represents an integer ofnot less than 1 and m>n, p represents 0 or 1, and t represents 1 or 2).

[0034] Furthermore, the present invention includes an oligomer or anactive particle, which comprises at least a polycondensate of the activemetal alkoxide.

BRIEF DESCRIPTION OF THE DRAWINGS

[0035]FIG. 1 shows ¹H-NMR spectrum of a compound obtained in the step(2) (ii) in Example 1.

[0036]FIG. 2 shows IR spectrum of the compound obtained in the step (2)(ii) in Example 1.

[0037]FIG. 3 shows ¹H-NMR spectrum of a compound obtained in the step(2) (i) in Example 3.

[0038]FIG. 4 shows IR spectrum of the compound obtained in the step (2)(i) in Example 3.

[0039]FIG. 5 shows ¹H-NMR spectrum of a compound obtained in the step(2) (ii) in Example 17.

[0040]FIG. 6 shows ¹H-NMR spectrum of a compound obtained in the step(2) (iii) in Example 21.

BEST MODE FOR CARRYING OUT OF THE INVENTION

[0041] The active component (or ingredient) of the present invention isused (or usable) in combination with a photosensitizer which constitutesa photosensitive resin composition, and has a unit for causing adifference in solubility owing to at least light exposure. Such anactive component comprises at least one member selected from the groupconsisting of the active metal alkoxide represented by the formula (1)or the polycondensate thereof, and the particle represented by theformula (2).

[0042] [Active Metal Alkoxide or a Polycondensate Thereof (1)]

[0043] (Active Metal Alkoxide (1a))

[0044] In the formula (1), the halogen atom represented by X includesfluorine, chlorine, bromine and iodine atoms. As the alkoxy group, theremay be exemplified a linear or branched chain C₁₋₁₀alkoxy group such asa methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, t-butoxy,pentyloxy, hexyloxy, heptyloxy, octyloxy and decyloxy group (preferablya C₁₋₆alkoxy group, more preferably a C₁₋₄alkoxy group). As thealkoxycarbonyl group, there may be exemplified a linear or branchedchain C₁₋₁₀alkoxy-carbonyl group such as a methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl,s-butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl andoctyloxycarbonyl group (preferably a C₁₋₆alkoxy-carbonyl group, morepreferably a C₁₋₄alkoxy-carbonyl group).

[0045] The alkoxy group or alkoxycarbonyl group may have a substituentsuch as a halogen atom, a hydrocarbon group which may have anunsaturated bond (an alkyl group, an alkenyl group, a cycloalkyl group,an aryl group, etc.), a heterocyclic group and an acyl group.

[0046] The metal atom whose valence is m, represented by M, is a metalwhose valence is not less than 2 (e.g., bivalent to quadrivalent) andwhich is capable of forming a metal alkoxide, for example, an alkalineearth metal (magnesium, calcium, etc.), a transition metal, a rare earthmetal or a metal element of the Groups 3 to 5 and 13 to 15 of thePeriodic Table of Elements. In particular, there may be mentioned ametal element of the Group 3 (such as yttrium), a metal element of theGroup 4 (such as titanium and zirconium), a metal element of the Group13 (such as aluminium), a metal element of the Group 14 (such assilicon), and the like. Preferred metal is titanium, zirconium,aluminium and silicon, especially silicon.

[0047] As the group Z, a group causing a difference in solubility bylight exposure may be mentioned, for example, (a) a photo-crosslinkablegroup or a photo-curable group, or (b) a hydrophilic group protected bya protective group.

[0048] As the (a) photo-crosslinkable or photo-curable group, there maybe exemplified azide group, cinnamoyl group, cinnamylidene group, apolymerizable group (a (meth)acryloyl group, allyl group, vinyl group,etc.) and the like. The polymerizable group and the crosslinkable groupare especially preferred.

[0049] As the hydrophilic group of the (b) hydrophilic group protectedby a protective group, there may be mentioned, a water- oralkali-soluble group (a group which imparts solubility by an action ofwater or an alkali), for example, in addition to an amino group and anN-substituted amino group (e.g., an N,N-diC₁₋₄alkylamino group) and thelike, a hydroxyl group, a carboxyl group and a sulfur-containingderivative group corresponding to the above-mentioned groups (includinga mercapto group, a thiocarboxyl group, a dithiocarboxyl group). Thehydroxyl group (including a phenolic hydroxyl group) and the carboxylgroup are especially preferable.

[0050] In the formula (1), n represents an integer of not less than 1(e.g., 1 to 3, especially 1 or 2). Incidentally, m is larger than n(m>n), and m minus n leaves 1 to 3 (m−n=1-3), preferably 2 or 3.

[0051] A first connecting unit U₁ and a second connecting unit U₂ arenot particularly restricted, and comprise an unit of various organicchains (e.g., a chain hydrocarbon, a hydrocarbon ring, a chainhydrocarbon having a hetero atom and a heterocycle) singly or incombination, and these organic chains may be connected through aconnecting (or binding) group. The chain hydrocarbon includes analiphatic hydrocarbon chain such as alkylene chain (e.g., a linear orbranched C₁₋₁₀alkylene chain such as an ethylene chain, a propylenechain, a trimethylene chain and a hexamethylene chain; a linear orbranched C₂₋₁₀alkenylene chain such as a vinylene chain, a propenylenechain, a isopropenylene chain and a butenylene chain; and the like). Thechain hydrocarbon having a hetero atom includes an alkylene chain (aC₂₋₁₀alkylene chain) containing at least one nitrogen atom in the mainchain, a thioether chain (a polythioC₂₋₁₀alkylene ether chain such as athioC₂₋₁₀alkylene ether chain and a dithioC₂₋₁₀alkylene ether chain), anether chain (a polyoxyC₂₋₁₀alkylene ether chain such as anoxyC₂₋₁₀alkylene ether chain and a dioxyC₂₋₁₀alkylene ether chain), andthe like. The hydrocarbon ring includes an aromatic C₆₋₁₂hydrocarbonring such as benzene; a cycloalkane ring (a monocyclic alicyclichydrocarbon ring), for example, a C₅₋₁₀cycloalkane ring such ascyclohexane; a crosslinked cyclic hydrocarbon ring (e.g., a bi- ortricycloalkane ring such as norbornane and adamantane; aC₅₋₁₀cycloalkene ring such as cyclohexene; a bi- or tricycloalkene ringsuch as norbornene); and the like. Moreover, a hydrocarbon ring may be aring in which a plurality of hydrocarbon rings may be connected througha hydrocarbon chain if necessary (biphenyl; a ring corresponding to abis(C₆₋₁₄aryl)C₁₋₄alkane such as diphenylmethane; etc.). For example,such a group may be exemplified as a group in which a chain hydrocarbongroup (a linear or branched C₂₋₄alkylene group or a linear or branchedC₂₋₄alkenylene group, etc.) connects with a hydrocarbon ring group (anarylene group, a cycloalkylene group, a bi- or tricycloalkylene group,etc.). The heterocycle includes a heterocycle containing at least oneheteroatom selected from oxygen, nitrogen and sulfur atoms, especially a5- or 6-membered heterocycle. Further, the chain or cyclic hydrocarbongroups or the heterocycles and so on may have a substituent such as analkyl group (e.g., a C₁₋₅alkyl group) and a halogen atom.

[0052] In the formula (1), the coefficient p for the first connectingunit U₁ is 0 or 1, and the coefficient t for the second connecting unitU₂ is an integer of not less than 1 (especially 1 or 2).

[0053] The connecting unit U₁ may be a unit represented by the followingformula (3a), and the connecting unit U₂ may be a unit represented bythe following formula (3b).

—(R¹)_(q)—(B)_(r)—  (3a)

—(R²)_(u)—(Ar)_(v)—  (3b)

[0054] (in the formula, each of the factors, R¹, R² and Ar, is eithersame or different, representing a bivalent hydrocarbon group, and Brepresents a bivalent bond such as an ester bond, a thioester bond, anamide bond, a urea bond, a urethane bond, a thiourethane bond and animino group; a bivalent atom such as an oxygen atom and a sulfur atom ora trivalent atom such as a nitrogen atom. Each of the factors, q, r, uand v, represents 0 or 1, and the total of q, r, u and v is not lessthan 1 (q+r+u+v≧1)).

[0055] Incidentally, when B is nitrogen atom and r=1, t is 1 or 2, andwhen B is an atom or a group other than nitrogen atom and r=1, t isusually 1.

[0056] As the bivalent hydrocarbon group represented by R¹, R² or Ar,there may be exemplified, a bivalent group corresponding to theabove-mentioned chain hydrocarbons (e.g., an alkylene group such as anethylene group, a propylene group and trimethylene group, an alkenylenegroup such as a vinylene group and an isopropenylene group) and abivalent group corresponding to the above-mentioned hydrocarbon rings(e.g., a cycloalkylene group, an arylene group (such as a phenylenegroup and a naphthalene group), a bi- or tricycloalkylene group, abiphenylene group, a group corresponding to a bisarylalkane) and thelike. Preferred R and R are a chain hydrocarbon group such as a linearor branched chain C₂₋₈alkylene group (especially a C₂₋₄alkylene group,etc.) and a linear or branched chain C₂₋₈alkylene group (especially aC₂₋₄alkylene group, etc.) and the like.

[0057] Preferred Ar is a hydrocarbon ring group, for example, an arylenegroup such as a phenylene group and a naphthalene group, a biphenylenegroup such as a biphenyl group, a bi- or tricycloalkylene group, a groupcorresponding to a bisarylalkane, and the like, and a C₆₋₁₂arylene group(a C₆₋₁₀arylene group) or C₅₋₈cycloalkylene group is especiallymentioned. The group Ar may have a substituent such as a halogen atom(e.g., fluorine atom, chlorine atom, bromine atom), an alkyl group(e.g., a C₁₋₄alkyl group), an alkoxy group (e.g., a C₁₋₄alkoxy group)and an acyl group (e.g., a C₁₋₄alkyl-carbonyl group).

[0058] In the formula, each of the factors, q, r, u and v, represents 0or 1, and the total of q, r, u and v is not less than 1 (q+r+u+v≧1), andusually, q plus r is 0 to 2 (q+r=0-2) and u plus v is 1 to 2 (u+v=1-2).

[0059] A unit (U₁)_(p)-(U₂-Z)_(t) containing the connecting unit is, forexample, represented by the following formula (3):

[(R ¹)_(q)—(B)_(r)]_(p)—[{(R²)_(u)—(Ar)_(v)}-Z]t (3)

[0060] (in the formula, R¹, R², B, Ar, p, q, r, t, u and v have the samemeanings defined above).

[0061] R¹ and R² may be exemplified the same group as theabove-mentioned, and usually, an alkylene group (especially aC₂₋₄alkylene group) or an alkenylene group (especially a C₂₋₄alkenylenegroup). B is an ester bond, an amide bond, a urea bond, a urethane bond,an imino group, a sulfur atom or a nitrogen atom, and Ar is usually ahydrocarbon ring group (e.g., a C₆₋₁₀arylene group or aC₅₋₈cycloalkylene group), especially a benzene ring or a cyclohexanering.

[0062] Such a metal alkoxide (1) may be obtained by a reacting of acompound having a unit (X)_(m−n)M^(m) with a compound having the groupZ, to form a connecting unit U between the metal M and the group Z, ormay be obtained by a reaction of a compound having a unit(X)_(m−n)-M^(m) [especially, (X)_(m−n)-M^(m)-(R¹)_(q)] with a compoundhaving a unit U₂-Z [especially, {(R²)_(u)—(Ar)_(v)}-Z]. Thus theconnecting unit U₁ is mostly a connecting or binding group formed bythese reaction, and the connecting unit U₂ is mostly derived from acompound having a unit U₂. Various reactions can be used for thereaction of each component, for example, there may be exemplified thefollowing reactions by a combination of the reactive groups.

[0063] (i) an ester bond- (or a thioester bond-) forming reaction of ahydroxyl group (or a mercapto group) or its lower alkyloxy group with acarboxyl group or its reactive derivative group (e.g., an acid anhydridegroup, an acid halide group, etc.); or a urethane bond- (or athiourethane bond-)forming reaction of a hydroxyl group (or a mercaptogroup) with an isocyanate group,

[0064] (ii) an ester bond- (or a thioester bond-) forming reaction of acarboxyl group or its reactive derivative group with a hydroxyl group(or a mercapto group) or its lower alkyloxy group; an ester bond-formingreaction of a carboxyl group with an epoxy group; an amide bond-formingreaction of a carboxyl group with an amino group; or a ring-openingreaction of a carboxyl group with an oxazoline ring,

[0065] (iii) an amide bond-(or an imino bond-) forming reaction of anamino group with a carboxyl group or its reactive derivative group(e.g., an acid anhydride group, etc.); a reaction of an amino group withan epoxy group (e.g., an imino bond-forming reaction, etc.); or a ureabond-forming reaction of an amino group with an isocyanate group,

[0066] (iv) an addition reaction of a hydroxyl group, a mercapto group,an amino group or a hydrogen atom (e.g., silyl group SiH), with a vinylgroup,

[0067] (v) Hech reaction of a halogen atom with a vinyl group (e.g., acoupling reaction of an alkene with a halogen-substituted aromaticcompound with the use of a palladium catalyst in the presence of abase).

[0068] For example, in the case where the metal M is a silicon atom, asa compound having the unit (X)_(m−n)M, there may be exemplified, atriC₁₋₄alkoxysilane such as trimethoxysilane, triethoxysilane and atripropoxysilane; a C₁₋₄alkyldiC₁₋₄alkoxysilane such asmethyldimethoxysilane and methyldiethoxysilane; aC₆₋₁₀aryldiC₁₋₄alkoxysilane such as phenyldimethoxysilane andphenyldiethoxysilane; and other silane compounds having a functionalgroup such as an isocyanate group, an epoxy group, an amino group, amercapto group, a hydroxyl group, a carboxyl group and an unsaturatedbond (e.g., especially, a silane coupling agent).

[0069] The silane coupling agent includes a compound represented by thefollowing formula (4):

(R⁶)_(u)Si(D)_(4−w)  (4)

[0070] (In the formula, R⁶ represents an organic group having a reactivegroup, D represents a hydrogen atom, a halogen atom (fluorine atom,chlorine atom, bromine atom and iodine atom) or OR⁷. R⁷ represents analkyl group having 1 to 4 carbon atoms and w is an integer of 0 to 2.).

[0071] As the organic group represented by R⁶ there may be mentioned analkyl group having a reactive group (e.g., an isocyanatealkyl group, acarboxyalkyl group, an epoxyalkyl group, an aminoalkyl group, amercaptoalkyl group, a hydroxyalkyl group; an alkyl group having apolymerizable group such as a vinyl group, an allyl group and a(meth)acryloyl group, etc.) or an aryl group having a reactive group(e.g., an isocyanatearyl group, a carboxyaryl group, an aminoaryl group,a hydroxyaryl group; an aryl group having a polymerizable group such asa vinyl group, an allyl group and a (meth)acryloyl group, etc.); and thelike. The alkyl group represented by R⁷, there may be exemplified methylgroup, ethyl group, butyl group, t-butyl group.

[0072] As an isocyanate group-containing silane coupling agent, theremay be mentioned an isocyanatoalkylalkoxysilane (e.g., anisocyanatoC₁₋₆alkylC₁₋₄alkoxysilane) such as1-isocyanatomethyl-1,1,1-trimethoxysilane, 1-(1- or2-isocyanatomethyl)-1,1,1-trimethoxysilane,1-isocyanatomethyl-1,1,1-triethoxysilane, 1-(1- or2-isocyanatoethyl)-1,1,1-triethoxysilane,1-isocyanatomethyl-1-methyl-1,1-dimethoxysilane,1-chloro-1-isocyanatomethyl-1,1-dimethoxysilane,1-(3-aminopropyl)-1-isocyanatoethyl-1,1-dimethoxysilane,1-(3-aminopropyl)-1-isocyanatoethyl-1,1-diethoxysilane,1-isocyanatomethyl-1-phenyl-1,1-dimethoxysilane,1-isocyanatopropyl-1-phenyl-1,1-dipropoxysilane, and the like.

[0073] As an epoxy group-containing silane coupling agent, there may bementioned an epoxyalkylalkoxysilane (e.g., an epoxy group-containing aC₃₋₈alkyl-C₁₋₄alkoxysilane) such as1-(1,2-epoxypropyl)-1,1,1-trimethoxysilane and1-glycidyl-1,1,1-trimethoxysilane; a glycidoxyalkylalkoxysilane (e.g., aglycidoxyC₁₋₆alkylC₁₋₄alkoxysilane) such as1-(3-glycidoxypropyl)-1,1,1-trimethoxysilane and1-(3-glycidoxypropyl)-1-methyl-1,1-dimethoxysilane; and others.

[0074] As an amino group-containing silane coupling agent, there may bementioned an amino group-containing silane coupling agent correspondingto the isocyanate group-containing silane coupling agent, especially, anaminoalkylalkoxysilane (e.g., an aminoC₁₋₆alkyl-C₁₋₄alkoxysilane) suchas 1-(3-N-(2′-aminoethyl)aminopropyl)-1-methyl-1,1-dimethoxysilane,1-(3-N-(2′-aminoethyl)aminopropyl)-1,1,1-trimethoxysilane and1-(3-aminopropyl)-1,1,1-trimethoxysilane.

[0075] As a mercapto group-containing silane coupling agent, there maybe mentioned a mercapto group-containing silane coupling agentcorresponding to the isocyanate group-containing silane coupling agent,especially, an alkoxysilane having a mercapto group (e.g., amercaptoC₁₋₆alkyl-C₁₋₄alkoxysilane) such as1-(3-mercaptopropyl)-1,1,1-trimethoxysilane and1-(3-mercaptopropyl)-1,1,1-triethoxysilane, and others.

[0076] Moreover, a hydroxy group-containing silane coupling agent and acarboxyl group-containing silane coupling agent, corresponding to theisocyanate group-containing silane coupling agent can be also utilized.

[0077] As a silane coupling agent having an unsaturated bond, there maybe mentioned a silane coupling agent having a polymerizable group suchas a vinyl group, an allyl group and a (meth)acryloyl group, etc. Thevinyl group-containing silane coupling agent includes1-vinyl-1,1-dimethyl-1-ethoxysilane,1-vinyl-1-methyl-1,1-diethoxysilane, 1-vinyl-1,1,1-trimethoxysilane,1-vinyl-1,1,1-triisopropenoxysilane,1-vinyl-1,1-dimethyl-1-chlorosilane, 1-vinyl-1-ethyl-1,1-dichlorosilane,1-vinyl-1,1,1-trichlorosilane,1-vinyl-1-methyl-1,1-bis(methylethylketoximine)silane,1-vinyl-1-methyl-1,1-bis(trimethylsiloxy)silane,1-vinyl-1-methyl-1,1-diacetoxysilane, 1-vinyl-1,1,1-triphenoxysilane,1-vinyl-1,1,1-tris(t-butylperoxy)silane, and others. Moreover, an allylgroup-containing silane coupling agent and a (meth)acryloyl group- (or a(meth)acryloyloxy group-) containing silane coupling agent,corresponding to the vinyl group-containing silane coupling agent can bealso utilized. Incidentally, as the silane coupling agent, acommercially available silane coupling agent can be also available.

[0078] As a compound having a photo-crosslinkable (or photo-curable)group or a compound having a hydrophilic group, corresponding to thecompound having group Z or a unit U₂-Z (especially, R²—Ar-Z), there maybe exemplified a compound having a reactive group [e.g., a group havingan active hydrogen atom such as a hydroxyl group, a carboxyl group andan amino group; an isocyanate group or a vinyl group (including a(meth)acryloyl group)], or a reactive atom (e.g., a halogen atom), inaddition to the photo-crosslinkable groups or the hydrophilic groups.

[0079] As a compound having a hydroxyl group, there may be exemplifiedan aliphatic polyhydroxy compound (e.g., a linear or branchedC₂₋₁₀alkylene glycol such as ethylene glycol, trimethylene glycol,propylene glycol and tetramethylene glycol; a polyoxyC₂₋₄alkylene glycolsuch as a di- to polyethylene glycol and a di- to polypropylene glycol),an aromatic polyhydroxy compound [e.g., a phenol such as hydroquinone,resorcin, catechol, phloroglucin, oxyhydroquinone, pyrogallol, analkylester of gallic acid (e.g., a C₁₋₄alkylester of gallic acid); ahydroxyaralkyl alcohol (e.g., a hydroxyC₆₋₁₀aryl-C₁₋₄alkyl alcohol) suchas xylylene glycol and hydroxybenzyl alcohol; a hydroxybenzophenone, ahydroxynaphthalene such as a naphthalene diol and a naphthalene triol; abiphenol, a bisphenol (e.g., a bisphenol A, a bisphenol F, a bisphenolAD, etc.)], an alicyclic polyhydroxy compound [a monocyclic alicyclicdiol (e.g., a C₅₋₈cycloalkanediol such as cyclohexanediol; aC₅₋₈cycloalkenediol such as a cyclohexenediol; a cyclohaxenedimethanol),a crosslinked alicyclic diol (e.g., a bi- or tricycloalkanediol such asa norbornanediol and an adamantanediol)], a heterocyclic polyhydroxycompound [a 5- to 8-membered unsaturated heterocyclic polyhydroxycompound (e.g., a 5- or 6-membered unsaturated heterocyclic di- ortrihydroxy compound) such as a dihydroxypyran and a dihydroxyfuran; a 5-to 8-membered saturated heterocyclic polyhydroxy compound (e.g., a 5- or6-membered saturated heterocyclic di- or trihydroxy compound, especiallya dihydroxyoxacycloalkane) such as a dihydroxytetrahydrofuran and adihydroxytetrahydropyran; etc.] a compound having a hydroxyl group and ahalogen atom (bromine atom, iodine atom, etc.) [e.g., a halogenatedalcohol (a halogenated C₁₋₁₀alkyl alcohol etc.), a halogenated phenol(e.g., a haloC₆₋₁₀aryl alcohol such as a bromophenol and an iodophenol),a halogenated cycloalkanol (e.g., a halogenated C₅₋₆cycloalkanol such asa iodohexanol)], a compound having a hydroxyl group and a carboxyl group[a hydroxycarboxylic acid, for example, ahydroxyaliphaticC₂₋₁₂carboxylic acid (e.g., a hydroxycaproic acid), ahydroxyaromaticC₆₋₁₀carboxylic acid (e.g., salicylic acid, adihydroxybenzoic acid, gallic acid, a hydroxynaphthoic acid), ahydroxyC₅₋₆cycloalkane-carboxylic acid (e.g., ahydroxycyclohexanecarboxylic acid)], a compound having a hydroxyl groupand an amino group [e.g., an aminoC₂₋₁₀alkyl alcohol such as anethanolamine and a propanolamine, an aminophenol (an aminoC₆₋₁₀arylalcohol such as an aminophenol, an aminocresol and an aminosalicylicacid, an aminoC₅₋₆cycloalkanol, etc.] a compound having a hydroxyl groupand an epoxy group (e.g., a glycidylC₆₋₁₀aryl alcohol such as aglycidylphenol), a compound having a hydroxyl group and a vinyl,(meth)acryloyl or allyl group (e.g., a vinylC₆₋₁₀aryl alcohol such as avinylphenol, a hydroxyC₂₋₆alkyl(meth) acrylate, an ally alcohol), andothers.

[0080] As a compound having a carboxyl group, there may be mentioned apolycarboxylic acid [e.g., a C₁₋₁₂alkane-dicarboxylic acid (e.g., adipicacid, pimelic acid, sebacic acid and azelaic acid), an aromaticdicarboxylic acid (e.g., a benzene dicarboxylic acid, a naphthalenedicarboxylic acid), a C₅₋₆cycloalkane-dicarboxylic acid (e.g., acyclohexanedicarboxylic acid)], a compound having a carboxylic group andan amino group [an aminoC₂₋₁₀alkyl-carboxylic acid, anaminoC₆₋₁₀aryl-carboxylic acid (e.g., an aminobenzoic acid), anaminoC₅₋₆cycloalkyl-carboxylic acid (e.g., an aminocyclohexanecarboxylicacid)], a compound having a carboxyl group and a halogen atom (e.g., ahalogenated aliphaticC₂₋₁₀carboxylic acid, a halogenatedC₆₋₁₀aryl-carboxylic acid such as a chlorobenzoic acid and aniodobenzoic acid, a halogenated C₅₋₆cycloalkyl-carboxylic acid such as achlorocyclohexanecarboxylic acid and an iodocyclohexanecarboxylic acid),a compound having a carboxyl group and an epoxy group (a glycidylgroup-containing C₆₋₁₀aryl-carboxylic acid such as a glycidylbenzoicacid), a compound having a carboxyl group and a vinyl, (meth)acryloyl orallyl group [e.g., a (meth)acrylic acid; a vinyl group-containingC₆₋₁₀aryl-carboxylic acid such as a vinylbenzoic acid; an unsaturatedpolycarboxylic acid such as itaconic acid, maleic acid and fumaric acidor a monoalkylester thereof; etc.], and the like.

[0081] As a compound having an amino group, there may be mentioned adiamine, for example, an aliphatic diamine [e.g., a C₂₋₁₀alkanediaminesuch as ethylenediamine, propylenediamine, 1,4-diaminobutane,hexamethylenediamine, 2,5-dimethylhexamethylenediamine), an aromaticdiamine (e.g., a C₆₋₁₀arylenediamine such as a methaphenylenediamine anddiaminodiphenylmethane; a xylylenediamine (aC₁₋₄alkyl-C₆₋₁₀arylene-C₁₋₄alkyl)diamine, etc.)], an alicyclic diamine(e.g. menthenediamine, isophorone diamine and a diaminoC₅₋₆cycloalkanesuch as a diaminodicyclohexylmethane), and the like.

[0082] As a compound having a halogen atom, there may be mentioned adihaloC₂₋₁₀alkane (such as a diiodohexane), a C₆₋₁₀aromatic dihalide(such as a diiodobenzene), a dihaloC₅₋₆cycloalkane (such as adiiodocyclohexane), and the like. As a compound having a vinyl group,there may be mentioned a C₆₋₁₀aromatic divinyl compound such as adivinylbenzene, and the like. As a compound having an isocyanate group,there may be mentioned an aliphatic diisocyanate such ashexamethylenediisocyanate; an aromatic diisocyanate such as atolylenediisocyanate and xylylenediisocyanate; an alicyclic diisocyanatesuch as isophoronediisocyanate; and the like.

[0083] In the case of using these compounds, it is easy to control theaffinity with a base resin and the solubility to a developer.Incidentally, in these compounds, a hydrophilic group HP (e.g., ahydroxyl group, a carboxyl group) may be protected by a protective groupPro in advance, before reacting it with a compound having a unit(X)_(m−n)M^(m), or may be protected by a protective group Pro afterreacting it with a compound having a unit (X)_(m−n)M^(m). That is, thegroup Z causing the difference in solubility may be a group —HP-Pro [inthe formula, HP means a hydrophilic group and Pro means a protectivegroup removing ((eliminating or leaving)) by light exposure and formingthe hydrophilic group (in particular, a protective group imparting ahydrophobicity to the hydrophilic group. Incidentally, the protectivegroup can be introduced by a conventional method, for example, variousmethods such as an acetalized reaction, an esterification method, anactive esterification method, a mixed acid anhydride method, an azidemethod, a method using a coupling agent (e.g., dicyclohexylcalboziimide(DCC) method, DCC-additive method, etc.), and the like.

[0084] As a protective group Pro of the hydrophilic group HP, there maybe mentioned a protective group for a hydroxyl group, for example, anacetal-series protective group such as an alkoxyalkyl group [e.g., aC₁₋₆alkoxy-C₁₋₆alkyl group (such as 1-methoxyetyl group, 1-ethoxypropylgroup and 1-methoxy-isopropyl group), preferably a C₁₋₄alkoxy-C₁₋₄alkylgroup); an acyl group such as an alkylcarbonyl group (e.g., aC₁₋₆alkyl-carbonyl group such as acetyl, propyonyl, isopropyonyl,butyly, t-butylcarbonyl group and isovaleryl group, preferably aC₁₋₄alkyl-carbonyl group), a cycloalkylcarbonyl group (e.g., aC₅₋₈cycloalkyl-carbonyl group such as cyclohexylcarbonyl group,preferably a C₅₋₆cycloalkyl-carbonyl group), an arylcarbonyl group(e.g., a C₆₋₁₀aryl-carbonyl group such as benzoyl group); aC₁₋₆alkoxy-carbonyl group (e.g., a C₁₋₄alkoxy-carbonyl group) such asmethoxycarbonyl group, ethoxycarbonyl group and t-butoxycarbonyl (t-BOC)group; an aralkyloxy carbonyl group such as benzyloxycarbonyl group(e.g., a C₆₋₁₀aryl-C₁₋₄alkyloxy-carbonyl group); a C₅₋₈cycloalkyl groupsuch as cyclohexyl group (e.g., a C₅₋₆cycloalkyl group); an aryl groupsuch as 2,4-dinitrophenyl group (e.g., a nitro group-substituted phenylgroup); an aralkyl group such as a benzyl group, a 2,6-dichlorobenzylgroup, a 2-nitrobenzyl group and a triphenylmethyl group (e.g., aC₆₋₁₀aryl-C₁₋₄alkyl group which may have a substituent); an acetal group(a diC₁₋₆alkoxy group such as a dimethoxy, diethoxy and1-methoxy-l-butoxy group); an oxacycloalkyl group such as atetrahydrofuranyl group and a tetrahydropiranyl group (e.g., a 5- to8-membered oxacycloalkyl group); a crosslinked cyclic alicyclichydrocarbon group such as a norbornyl group, an admantyl group and ahydrogenated naphthyl group (e.g., a bi- to tetracycloalkyl group), andthe like.

[0085] Further, as a protective group for a carboxyl group, there may bementioned, for example, a C₁₋₆alkyl group (e.g., a C₁₋₄alkyl group) suchas methyl group, ethyl group and t-butyl group; a carbamoyl group whichmay have a substituent (e.g., an alkyl group, an aryl group,etc.)(carbamoyl group; a C₁₋₆alkyl-carbamoyl group such asmethylcarbamoyl group and ethylcarbamoyl group (preferably aC₁₋₄alkyl-carbamoyl group); a C₆₋₁₀arylcarbamoyl group such asphenylcarbamoyl group); a crosslinked cyclic alicyclic hydrocarbon groupsuch as a norbornyl group, an admantyl group and a hydrogenated naphthylgroup (e.g., a bi- to tetracycloalkyl group); adiC₁₋₄alkylphosphinothioyl group such as a dimethylphosphinothioylgroup; a diC₆₋₁₀arylphosphinothioyl group such as adiphenylphosphinothioyl group; and the like.

[0086] In particular, the protective group Pro is preferable to be ahydrophobic protective group which imparts hydrophobicity to thehydrophilic group HP. As the protective group for a hydroxyl group, thefollowing groups are preferred, for example, an acyl group (especially,a C₁₋₄alkyl-carbonyl group such as t-butylcarbonyl group), analkoxycarbonyl group (a C₁₋₄alkoxycarbonyl group such as t-BOC group), a5- or 6-membered oxacycloalkyl group (such as a tetrahydropiranylgroup), a bi- or tricycloalkyl group (such as a norbornyl group and anadmantyl group), a C₁₋₄alkoxy-C₁₋₄alkyl group. As the protective groupfor a carboxyl group, the following groups are preferred, for example,an alkyl group (a C₁₋₄alkyl group such as a t-butyl group), a carbamoylgroup which may have a substituent; a crosslinked cyclic alicyclichydrocarbon group such as a norbornyl group, an admantyl group and ahydrogenated naphthyl group (e.g., a bi- to tetracycloalkyl group).

[0087] In each of the above-mentioned reactions, a conventional catalystor solvent can be utilized if necessary. As the catalyst, depending onthe species of the reactions, there may be used, for example, an acid(e.g., an inorganic acid such as hydrochloric acid and sulfuric acid; anorganic acid such as p-toluenesulfonic acid), a base (e.g., an organicamine such as tertiary amine, etc.), a conventional catalyst foracetalization (e.g., hydrogen chloride, manganese dioxide, sulfuricacid, etc.), and a catalyst for addition reaction (e.g., a transitionmetal catalyst such as a palladium catalyst). As the solvent, there maybe used, for example, water, an organic solvent such as an alcohol, aglycol, a cellosolve, a ketone, an ester, an ether, an amide, ahydrocarbon, a halogenated hydrocarbon, a carbitol and an ester ofglycol ether (e.g., a cellosolve acetate and propylene glycol monomethylether acetate). Incidentally, in the case of using a component having anisocyanate group, for example, the reaction is preferably conducted in acondition where activity of the isocyanate group can be maintained(e.g., in the absence of moisture, or in the presence of moisture at aamount which does not substantially interfere the activity of theisocyanate group, especially, in nonaqueous system).

[0088] In the formula (1), the following combinations may be mentionedas a preferable combination of groups:

[0089] X: a C₁₋₄alkoxy group, a halogen atom (especially, a C₁₋₂alkoxygroup),

[0090] Z: a hydroxyl or carboxyl group protected by a hydrophobicprotective group which is capable of removing (removable) owing to lightexposure,

[0091] M: a metal atom selected from the group consisting of aluminum,titanium, zirconium and silicon,

[0092] (U₁)_(p)-(U₂-Z)_(t): a unit represented by the above-mentionedformula (3),

[0093] n=1 or 2,

[0094] p=0 or 1 (q+r=0 to 2), and

[0095] t=1 or 2 (u+v=1 to 2)

[0096] (Polycondensate or Active Particle of an Active Metal Alkoxide(1b))

[0097] An active component (especially an active particle) of thepresent invention may comprise a polycondensate of the above-mentionedactive metal alkoxide. Such an active component may be an activeparticle in the form of a particulate (particulate matter), or a liquidor solid oligomer. The active component, the polycondensate of theactive component can be obtained by polycondensing the active metalalkoxide by a conventional sol-gel method to form of a polymer or a sol.

[0098] More concretely, the process for producing the active componentcomprises dissolving a metal alkoxide component comprising at least anactive metal alkoxide to an organic solvent, adding water thereto andstirring the mixture in the presence of a polymerizable catalyst. As theorganic solvent, such a hydrophilic or water-soluble solvent can beused, for example, an alcohol (e.g., methanol, ethanol and isopropanol),a ketone (e.g., acetone), an ester [e.g., ethyl acetate; an ester oflactic acid such as ethyl lactate; a (poly)oxyalkylene glycol alkylether acetate such as propylene glycol methyl ether acetate (PGMEAetc.); etc.], a cellosolve (e.g., a methylcellosolve, a ethylcellosolveand a butylcellosolve), and the like. These solvents may be same with asolvent of a resist solution (e.g., ethyl lactate and PGMEA).

[0099] The proportion of water is, relative to 1 mol of the metal atomin the metal alkoxide component, about 0.1 to 10 mmol, preferably about0.2 to 5 mmol and more preferably about 0.5 to 2 mmol.

[0100] As the polymerizable catalyst, there may be used, for example, anacid (e.g., an inorganic acid such as hydrochloric acid, sulfuric acid,nitric acid and a phosphoric acid; an organic acid such as a aceticacid; etc.), or a base (e.g., an inorganic base such as an ammonia, anorganic base such as an amine, etc.), and the like. The proportion ofthe catalyst is, relative to 1 mol of metal atom in the metal alkoxidecomponent, about 0.001 to 0.1 mmol, preferably about 0.005 to 0.05 mmol.

[0101] The polymerization temperature may be about 0 to 40° C. (e.g., 10to 35° C.), preferably a room temperature (about 15 to 30° C.). Thepolymerization pressure is not especially limited, may be normalpressure (or atmospheric pressure), increased pressure (pressurization),or reduced pressure (depressurization), usually normal pressure. Thepolymerization time is not especially limited, may be selected withinthe wide range from 5 minutes to 1 day, and is preferably from 10minutes to 12 hours, preferably from 30 minutes to 10 hours.

[0102] The metal alkoxide component may comprise a metal alkoxiderepresented by the following formula (5) in addition to the active metalalkoxide. That is, the active metal alkoxide may be copolycondensed withthe metal alkoxide (5).

(X)_(m−n−1)M^(m)(R⁵)_(n−1)  (5)

[0103] (In the formula, R⁵ represents a hydrogen atom or an alkyl group.X, M, m and n have the same meanings defined above.)

[0104] In the formula (5), an alkyl group represented by R⁵ may beexemplified by the alkyl groups similar to those mentioned above,especially a methyl group or an ethyl group is preferable. X is usuallya halogen atom or an alkoxy group.

[0105] In the case of copolycondensing with the metal alkoxide (5), theweight ratio of an active metal alkoxide (1) relative to a metalalkoxide (5) can be selected within the range of, for example, about5/90 to 90/10 (e.g., about 10/90 to 90/10), and is usually about 5/90 to80/20 (e.g., about 5/95 to 60/40), preferably about 10/90 to 50/50, andmore preferably about 20/80 to 40/60.

[0106] The mean particle size of the particulate active component(active particle) can be adjusted by a degree of polymerization,depending on the degree of miniaturization of a pattern, for example,can be selected from the range of about 1 to 500 nm (e.g., about 1 to100 nm), preferably 1 to 50 nm in accordance with BET method. Thepreferred mean particle size of the active particle is usually about 2to 30 nm and preferably about 3 to 25 nm (e.g., about 5 to 25 nm). Inparticular, since making the smaller mean particle size of the activeparticle ensures thinning a photosensitive layer, resolution can beimproved as much as edge roughness can be reduced. Further, when themean particle size of the active particle is smaller than an exposingwavelength, because the active particle is substantially transparent tothe exposing wavelength, light exposure can be conducted to the depth ofthe photosensitive layer even if the layer is thickened, and as aresult, sensitivity and resolution can be improved as much as a patternwith high sensitivity and high resolution can be formed in regard to alight source of shorter wavelength.

[0107] [Active Particle (2) Having a Fine Particle Carrier]

[0108] The particle represented by the formula (2) comprises a fine(minute) particle carrier and a unit which directly or indirectly bondsto the carrier and causes a difference in solubility by light exposure(especially, a unit which can become hydrophilic by removing(eliminating or leaving) a protective group by light exposure). In theunit, the protective group can be usually removed (eliminated) inassociation with a photosensitizer by light exposure.

[0109] In the above-mentioned formula (2), the connecting unitrepresented by U₁ and U₂, and the group represented by Z may beexemplified by the connecting unit and the group Z or coefficientsmentioned in the section of the formula (1), the coefficient p and thave the same meanings defined above.

[0110] The active particle may be a particle in which s and p are s=p=0in the formula (2) (e.g., a particle wherein a hydrophilic group of afine particle carrier such as an organic fine particle is protected by aprotective group), or a particle in which at least one factor selectedfrom s and p is 1. Moreover, in the formula (2), k is a value whichdepends on a concentration of a reactive group (e.g., a hydrophilicgroup) of carrier and an introduction amount of the group Z by thecoupling agent. Incidentally, the coupling agent usually corresponds toa compound having a metal atom M in the formula (1).

[0111] More concretely, there may be mentioned the case in which thegroup Z is a hydrophilic group HP protected by a protective group Pro.For example, in a carrier P having a reactive group, (a) in the casewhere the reactive group is a hydrophilic group, the hydrophilic groupmay be protected by a protective group (s=p=0), and (b) in the casewhere the reactive group is not a hydrophilic group, the hydrophilicgroup HP may be protected by a protective group Pro by introducing thehydrophilic group HP through a connecting unit U₁ and/or a connectingunit U₂ (s=0, p=1 and/or t=1). Moreover, in the case where the carrier Pis a fine particle such as an inorganic fine particle, the reactivegroup may be introduced with the use of a coupling agent, and (c) in thecase where the reactive group is a hydrophilic group HP, thishydrophilic group HP may be protected by the protective group Pro (s=1,t=0), (d) in the case where the introduced reactive group is not ahydrophilic group, the hydrophilic group HP may be protected by aprotective group Pro by introducing a hydrophilic group HP through aconnecting unit U₁ (s=1, p=1, t=1). Incidentally, in the presentspecification, a unit—U₂-HP— is sometimes referred to as ahydrophilizable unit.

[0112] As the reaction of each component, i.e., the fine particlecarrier P, the coupling agent Y, the connecting units U₁ and U₂, variousreactions may be utilized, and there may be mentioned, for example, areaction by the above-mentioned combinations of the reactive groups,concretely, a method which can be utilized for a reaction of a compoundhaving the unit (X)_(m−n)M^(m) or (X)_(m−n)-M^(m)-(R¹)_(q) with acompound having the group Z or a compound having the unit U₂-Z or{(R²)_(u)—(Ar)_(v)}-Z, for example, (i) the ester bond-(thioester bond-)forming reaction, or the urethane bond- (or a thiourethane bond-)forming reaction, (ii) the ester bond- (or a thioester bond-) formingreaction, the amide bond-forming reaction or the ring-opening reaction,(iii) the amide bond- (or an imino bond-) forming reaction, the reactionof an amino group with an epoxy group (e.g., an imino bond-formingreaction, etc.) or the urea bond-forming reaction, (iv) the additionreaction, and (v) the coupling reaction such as Hech reaction.

[0113] Hereinafter, the case introducing a hydrophilic group into aninorganic fine particle through both a coupling agent and a connectingunit is taken as an example and explained. For example, each componentmay be bonded by reacting a connecting unit U having two hydroxyl groups(e.g., a dihydroxy compound such as resorcin) with a coupling agent Yhaving an isocyanate group (e.g., a silane coupling agent) to form acompound having a free hydroxyl group and a coupling group (an alkoxygroup or a halogen atom), wherein the coupling agent is bonded to one ofhydroxyl groups of the unit; protecting the free hydroxyl group by aprotective group such as t-BOC group; and then reacting an inorganicfine particle carrier (e.g., silicasol, etc.) with the coupling group(the alkoxy group or the halogen atom). Further, for example, otherprocesses may be employed, that is, protecting a hydroxyl group of acompound having a halogen atom (iodine atom, bromine atom, etc.) and ahydroxyl group (e.g., a halogen-containing aromatic hydroxy compoundsuch as 4-iodophenol) by a protective group such as t-BOC group inadvance; subjecting the resultant compound to a coupling reaction with avinyl group-containing silane coupling agent (e.g.,methacryloxypropyltrimethoxysilane) by Hech reaction to bind thecompound with an inorganic fine particle carrier via the alkoxy group orhalogen atom site in the silane coupling agent. Incidentally, the orderof each reaction among each component is not particularly limited, forexample, a carrier may be reacted with a coupling agent in advance andthen the resultant may be reacted with other components. Moreover, inthe case of using a component having an isocyanate group, for example,the reaction is preferably conducted under the condition where theactivity of the isocyanate group can be maintained (e.g., in the absenceof moisture, or in the presence of moisture at a amount which does notsubstantially interfere the activity of the isocyanate group,especially, in nonaqueous system).

[0114] In each reaction step, a conventional catalyst or a solvent maybe used if necessary. As the solvent, there may be used, for example,water, an organic solvent such as an alcohol, a glycol, a cellosolve, aketone, an ester, an ether, an amide, a hydrocarbon, a halogenatedhydrocarbon, a carbitol and an ester of glycol ether (e.g., a cellosolveacetate and a propylene glycol monomethyl ether acetate).

[0115] Hereinafter, as a typical active component shown in the formula(2), a active particle, in which the group Z is a hydrophilic group HPprotected by the protective group Pro, is taken as an example andexplained.

[0116] As the hydrophilic group HP, there may be exemplified a water- oralkali-soluble group such as hydroxyl group, carboxyl group and asulfur-containing derivative group thereof (e.g., mercapto group, athiocarboxyl group and dithiocarboxyl group), in addition to amino groupand an N-substituted amino group (e.g., a N,N-diC₁₋₄alkylamino group)and the like, and especially, the hydroxyl group (e.g., a phenolichydroxyl group) and the carboxyl group are preferred.

[0117] As the fine particle carrier P, an organic fine particle [athermoplastic resin which may be crosslinked (e.g., a styrenic resinwhich may be crosslinked such as a crosslinked polystyrene, astyrene-(meth)acrylic acid copolymer and a styrene-maleic anhydridecopolymer; an (meth)acrylic resin which may be crosslinked such as acrosslinked polymethyl methacrylate and a methylmethacrylate-(meth)acrylic acid copolymer; a silicone resin; athermosetting resin which may be crosslinked or cured such as apolyamide resin, a crosslinked melamine resin and a crosslinkedguanamine resin, etc.) can be also employed. The fine particle carrier Pmay have a hydrophilic group such as a hydroxyl group and a carboxylgroup, and the concentration of these hydrophilic groups may be adjustedaccording to the amount to be used of a monomer having the hydrophilicgroup. It is advantageous to use an inorganic fine particle forimproving the properties such as heat resistance and dry etchingresistance.

[0118] As the inorganic fine particle carrier, for example, there may beutilized, a metal alone (simple or single metal) (e.g., gold, silver,copper, platinum, aluminium), an inorganic oxide (e.g., silica (e.g.,silica sol such as colloidal silica, aerogels, glass), alumina, titania,zirconia, zinc oxide, copper oxide, lead oxide, yttrium oxide, tinoxide, indium oxide, magnesium oxide), an inorganic carbonate (e.g.,calcium carbonate and magnesium carbonate), an inorganic sulfate (e.g.,barium sulfate and calcium sulfate), a phosphate (e.g., calciumphosphate and magnesium phosphate), and the like. The inorganic fineparticle carriers include sols and gels prepared by, for example, asol-gel method. These inorganic fine particle carriers can be usedeither singly or in combination.

[0119] Use of the fine particle carriers enhances development efficiencyby a developer because developers may be permeated (infiltrated) betweenfine particles.

[0120] The shape of the fine particle carriers is not limited to sphereand may be spheroid, disk, rod-like, or fibrous. The mean particle sizeof the fine particle carriers, depending on the degree of minuteness ofa pattern to be formed, for example, can be selected within the range ofabout 1 to 1,000 nm, preferably 5 to 500 nm (e.g., 1 to 100 nm) and morepreferably 1 to 50 nm (e.g., 5 to 50 nm) in accordance with the BETprocess. In particular, since making the smaller mean particle size ofthe active particle ensures thinning a photosensitive layer, resolutioncan be improved as much as edge roughness can be reduced. Further, whena fine particle carrier (e.g., silicasol) having smaller mean particlesize of the active particle than an exposing wavelength is used, becausethe active particle is substantially transparent to the exposingwavelength, light exposure can be conducted to the depth of thephotosensitive layer even if the layer is thickened, and as a result,sensitivity and resolution can be improved as much as a pattern withhigh sensitivity and high resolution can be formed in regard to a lightsource of shorter wavelength. Incidentally, such a silicasol iscommercially available as an organosol (an organosilicasol). Forexample, the organosol is available from Nissan Chemical Industries,Ltd. as the tradename “Snowtex collidalsilica”.

[0121] As a coupling agent corresponding to a residue Y of the couplingagent, for example, there may be exemplified an organic metal compoundcontaining, as the metal M, an alkaline earth metal, a transition metal,a rare earth metal, or a metal element of the Groups 3 to 5 and 13 to 15of the Periodic Table of Elements, especially a metal element of theGroups 4, 13 and 14 of the Periodic Table of Elements, for example,aluminium, titanium, zirconium, silicon. Among the organic metalcompounds, a titanium coupling agent and a silane coupling agent(especially the silane coupling agent) are preferred.

[0122] The silane coupling agent includes the coupling agentsrepresented by the formula (4). The reactive group D corresponding tothe fine particle carrier of the coupling agent (4) is usually a halogenatom (bromine atom, chlorine atom, etc.), a hydrolytic condensable groupsuch as an alkoxy group (e.g., a C₁₋₄alkoxy group such as methoxy groupand ethoxy group, especially a C₁₋₂alkoxy group) represented by OR⁷ (R⁷represents a C₁₋₄alkyl group).

[0123] The silane coupling agent includes the above-mentioned couplingagents [e.g., the isocyanate group-containing silane coupling agents,the epoxy group-containing silane coupling agents, the aminogroup-containing silane coupling agents, the mercapto group-containingsilane coupling agents, the hydroxyl group-containing and carboxylgroup-containing silane coupling agents corresponding to the isocyanategroup-containing silane coupling agents, the vinyl group-containingcoupling agents, the allyl group-containing silane coupling agents andthe (meth)acryloyl group-containing silane coupling agents].

[0124] As the organic metal compound containing, as the metal M,aluminium, titanium or zirconium, there may be exemplified the organicmetal compounds corresponding to the above-mentioned silane couplingagents.

[0125] The ratio of the coupling agent relative to the inorganic fineparticle carrier can be selected from the range of, for example, about0.1 to 200 parts by weight, preferably about 0.5 to 150 parts by weight,more preferably about 1 to 100 parts by weight relative to 100 parts byweight of the inorganic fine particle carrier.

[0126] The connecting unit U includes the above-mentioned units [e.g., aunit containing a chain hydrocarbon (e.g., a linear or branchedC₁₋₁₀alkylene chain such as a C₂₋₆alkenylene chain), a hydrocarbon ring(an aromatic C₆₋₁₂hydrocarbon ring such as a benzene ring (e.g., anaromatic C₆₋₁₀hydrocarbon ring), a C₅₋₁₀cycloalkane ring, aC₅₋₁₀cycloalkene ring, a crosslinked cyclic hydrocarbon ring (e.g., abi- or tricycloalkane ring), a ring wherein a plurality of hydrocarbonchains and/or hydrocarbon rings are bonded (e.g., aC₆₋₁₄aryl-C₁₋₄alkyl-C₆₋₁₄aryl, etc.), a heterocycle (e.g., a heterocyclecontaining at least one hetero atom selected from an oxygen atom, anitrogen atom and a sulfur atom)].

[0127] The connecting unit U may have a substituent as far as thecharacteristic of the active component is not inhibited. Incidentally,in the case where the unit has a substituent (e.g., an alkyl group, acycloalkyl group and an aryl group), affinity to or compatibility with abase resin can be improved and uniform dispersion of the activecomponent in the photosensitive resin composition can be attained, andalso, the difference in solubility between exposed-area and non-exposedarea relatively seems to be enlarged.

[0128] The compound corresponding to the hydrophilizable unit (-U₂-HP—)includes a compound having an active hydrogen atom such as a hydroxylgroup, a carboxyl group and an amino group, for example, theabove-exemplified compounds [e.g., a compound having plural hydroxylgroups, a compound having plural carboxyl groups, a compound having ahydroxyl group and a carboxyl group, a compound having a hydroxyl groupand an amino group, a compound having a carboxyl group and an aminogroup]. The compound may have a reactive halogen atom like theabove-exemplified compounds having a halogen atom. Moreover, thecompound may be the above-exemplified compound having an isocyanategroup.

[0129] With using such a compound, affinity to a base resin orsolubility to a developer is easy to control. Incidentally, in thesecompounds, as mentioned above, the hydrophilic group HP (e.g., ahydroxyl group and a carboxyl group) may be protected by the protectivegroup Pro in advance, or may be protected by the protective group Proafter introduction of the hydrophilic group HP. As the protective groupPro for the hydrophilic group HP, there may be mentioned theabove-exemplified protective groups.

[0130] In particular, a hydrophobic protective group which impartshydrophobicity to the hydrophilic group is preferable. For example, as aprotective for a hydroxyl group, the following groups are preferable, anacyl group (especially an alkylcarbonyl group such as a t-butylcarbonylgroup), an alkoxycarbonyl group (a C₁₋₆alkoxycarbonyl group such ast-BOC group), an acetal group (e.g., a diC₁₋₆alkoxy group), a 5- or6-membered oxacycloalkyl group (e.g., a tetrahydropiranyl group), a bi-or tricycloalkyl group (e.g., a norbornyl group and an adamantyl group),a C₁₋₄alkoxy-C₁₋₄alkyl group and the like. As a protective group for thecarboxyl group, an alkyl group (a C₁₋₄alkyl group such as t-butylgroup), a carbamoyl group which may have a substituent and a bi- ortricycloalkyl group (e.g., a norbornyl group and an adamantyl group) arepreferred.

[0131] Thus, also in the particle represented by the formula (2), thegroup Z to cause (generate) the difference in solubility is usually agroup —HP-Pro [in the formula, HP represents a hydrophilic group, Prorepresents a protective group forming the hydrophilic group HP byremoving (eliminating or leaving) owing to light exposure (especially, aprotective group which imparts hydrophobicity to the hydrophilic groupHP)].

[0132] In the particle represented by the formula (2), as a combinationof preferable groups, the following combinations may be exemplified.

[0133] P: an inorganic fine particle,

[0134] Y: a silane coupling residue,

[0135] (U₁)_(p)-(U₂-Z)_(t): a unit represented by the above-mentionedformula (3),

[0136] Z: a group —HP-Pro (in the formula, HP represents a hydrophilicgroup (especially a hydroxyl group or a carboxyl group), Pro representsa protective group which imparts hydrophobicity to the hydrophilic groupHP and causes (generates) the hydrophilic group HP by removing(eliminating or leaving) owing to light exposure,

[0137] s: 1,

[0138] p; 0 or 1, and

[0139] t: an integer of not less than 1 (especially 1 or 2).

[0140] The especially preferable particle comprises a connecting unitbonding to an inorganic fine particle having a mean particle size of 1to 50 nm through a silane coupling agent; a hydrophilic group bonding tothe connecting unit; and a protective group protecting the hydrophilicgroup, and the group Z which causes the difference in solubility bylight exposure comprises the hydrophilic group(s) and the protectivegroup(s). Moreover, the connecting unit usually comprises at least onemember selected from the group consisting of an aromaticC₆₋₁₂hydrocarbon ring, a monocyclic alicyclic hydrocarbon ring, acrosslinked alicyclic hydrocarbon ring and an aliphatic hydrocarbonchain, and the hydrophilic group is a hydroxyl group or a carboxylgroup. Further, the protective group is usually (i) a protective groupfor the hydroxyl group selected from a C₁₋₄alkyl-carbonyl group, aC₁₋₄alkoxy-C₁₋₄alkyl group, a C₁₋₄alkoxy-carbonyl group, a 5- or6-membered oxacycloalkyl group and a bi- or tricycloalkyl group, or (ii)a protective group for the carboxyl group selected from a C₁₋₄alkylgroup, a carbamoyl group, a C₁₋₄alkyl-carbamoyl group, aC₆₋₁₀aryl-carbamoyl group and a bi- or tricycloalkyl group.

[0141] Incidentally, the particle represented by the formula (2) may bea particle wherein the active metal alkoxide binds to theabove-exemplified fine particle carrier. That is, the particle may be aparticulate active component obtained by a coupling reaction of the fineparticle carrier with the active metal alkoxide represented by theformula (1) with the use of the group X (e.g., an alkoxy group, ahalogen atom, etc.) in the active metal alkoxide represented by theformula (1).

[0142] [Active Component]

[0143] The active component (or the photoactive component) of thepresent invention is advantageously used (usable) in combination with aphotosensitive resin composition. The active component, i.e., the activemetal alkoxide or its polycondensate (an oligomer or an active particle)represented by the formula (1) and an active particle represented by theformula (2), can be utilized either singly or in combination.

[0144] When the active component (1) is used (usable) in combinationwith a photosensitizer of a photosensitive resin composition, because ofthe group Z of the active metal alkoxide, which is introduced into theactive component, a difference in solubility can be caused (made orgenerated) by light exposure. For example, (a) in the case where thegroup Z is a photosensitive group such as a crosslinkable group, whenthe active component is applied to a negative resist in combination witha photosensitizer such as a photoactive acid generator and acrosslinking agent, a photopolymerization initiator, crosslinking orpolymerization occurs in an exposed area to inhibit dissolution in theexposed area, and as a result, the difference in solubility betweenexposed area and non-exposed area occurs.

[0145] Further, in the active component (1), (2), the protective groupis capable of removing (removable) by light exposure, especially inassociation with a photosensitizer constituting a photosensitive resincomposition by light exposure. (b) In the case where the group Z is ahydrophilic group protected by a protective group capable of removing(removable) owing to light exposure, the protective group is eliminated(or deprotected) by light exposure (especially, in association with aphotosensitizer owing to light exposure) to cause (make) a hydrophilicgroup such as a hydroxyl group or a carboxyl group, by using the activecomponent in combination with a photosensitizer such as a photoactiveacid generator. Consequently, when the active component is applied to,especially, a positive resist, a hydrophilic group such as a hydroxylgroup and a carboxyl group is caused (generated) and dissolution by adeveloper is accelerated in an exposed area, and dissolution can berestrained by enhancing an affinity to a base resin by an action of theprotective group (especially a hydrophobic protective group) in anon-exposed area, resulting in enlarging the difference in dissolutionrate between the exposed area and the non-exposed area. In particular,use of a hydrophobic group as the protective group, can realize drasticrestraint of solubility in the non-exposed area as well as restraint ofswelling of resist with development, resulting in improvement ofresolution, even when the particle P in the formula (2) is an inorganicfine particle carrier with high hydrophilicity such as a silicasol. Theremoval (elimination) of the protective group mostly occurred inrelation to (in association with) the photosensitizer, especially bycatalytic action of an acid. As such an acid, an acid generated by lightexposure (especially an acid generated from a photoactive acid generatorconstituting a photosensitive resin composition) is advantageouslyutilized.

[0146] [Photosensitive Resin Composition]

[0147] Although the photosensitive resin composition (or a resistcomposition) of the present invention may comprise a photosensitizer andthe above-mentioned active component, usually it comprises a base resin(an oligomer or a polymer), a photosensitizer and the above-mentionedactive component. The photosensitive resin composition can be developedby an organic solvent (e.g., an alcohol), but usually the photosensitiveresin is preferred to be capable of water- or alkali-development. Apositive photosensitive resin composition which can be developed bywater or an alkali aqueous solution is especially preferable.

[0148] As the base resin, there may be exemplified a polymer having apolar group, for example, a hydroxyl group-containing polymer [e.g., apolyvinyl acetal, a polyvinyl alcohol, an ethylene-vinylalcoholcopolymer, a hydroxyl group-containing cellulose derivative (e.g., ahydroxyethyl cellulose), a polyvinyl phenolic resin and a novolak resin(e.g., a phenol novolak resin)], a carboxyl group-containing polymer[e.g., a homo- or copolymer comprising a polymerizable unsaturatedcarboxylic acid (e.g., a (meth)acrylic acid, maleic anhydride anditaconic acid) and a carboxyl group-containing cellulose derivative(e.g., a carboxyl methylcellulose or its salt)], an estergroup-containing polymer [e.g., a homo- or copolymer of a monomer suchas a vinylester of carboxylic acid (e.g., a vinyl acetate) and an esterof (meth)acrylic acid (e.g., a methyl methacrylate) (e.g., a polyvinylacetate, an ethylene-vinyl acetate copolymer and a (meth)acrylic resin)and a polyester, a cellulose ester, etc.], a ether group-containingpolymer [e.g., a polyalkylene oxide, a polyoxyalkylene glycol, apolyvinyl ether-series resin, a silicon-containing resin, a celluloseether, etc.], a carbonate group-containing polymer, an amide orN-substituted amide group-containing polymer [e.g., a polyvinylpyrrolidone, a polyurethane-series polymer, a polyurea, a nylon or apolyamide-series polymer [e.g., a polyamide using a lactam component, adicarboxylic acid component or a diamine component (e.g., nylon 66,nylon 6, a modified nylon, a star-burst dendrimer (D. A. Tomalia. etal., Polymer Journal, 17,117 (1985)), etc.); apoly(meth)acrylamide-series polymer; a polyamino acid; a polymer havinga biuret bond; a polymer having an allophanate bond; and a protein suchas gelatin], a polymer having a nitrile group (e.g., anacrylonitrile-series polymer), a polymer having a glycidyl group (anepoxy resin, a homo- or copolymer of glycidyl (meth)acrylate, etc.), ahalogen-containing polymer (e.g., a polyvinyl chloride, a vinylchloride-vinyl acetate copolymer, a vinylidene chloride-series polymerand a chlorinated polypropylene), a polymerizable oligomer or polymer(e.g., an oligomer or polymer having a polymerizable group such as a(meth)acryloyl group, an allyl group, a vinyl group and a cinnamoylgroup), and the like. The base resin may be utilized either singly or incombination of two or more species.

[0149] Incidentally, to enhance the sensitivity against exposure beamsof a shorter wavelength, a resin having high transparency to theexposure beam (e.g., a non-aromatic resin such as a alicyclic resin) maybe utilized as the base resin. In the case using the non-aromaticphotosensitive resin (composition), utilization of exposure sources ofshorter wavelength can be achieved as well as formation (orconstitution) of minuter patterns.

[0150] As the polymerizable oligomer or resin constituting a negativeresist, there may be usually exemplified an epoxy(meth)acrylate, apolyester (meth)acrylate, an unsaturated polyester resin, a polyurethane(meth)acrylate, a polymerizable polyvinyl alcohol-series polymer (e.g.,a product in a reaction of a polyvinyl alcohol with an N-methylolacrylamide), and the like. The non-polymerizable resin constituting anegative resist includes a polyvinylphenol-series resin (e.g., ahomopolymer of a vinylphenol, a copolymer of a vinylphenol with othercopolymerizable monomer(s)), a polyamide-series polymer, a siliconeresin-based polymer (a silicone resinous polymer), and the like. As thecopolymerizable monomer, there may be exemplified, for example, anacrylic monomer (a (meth)acrylic acid, a C₁₋₄alkyl(meth)acrylate such asmethyl methacrylate, a hydroxyC₂₋₄alkyl(meth)acrylate such ashydroxyethyl methacrylate, a glycidyl (meth)acrylate), a styrenicmonomer such as styrene, and the like.

[0151] In the negative resist, if necessary, a polymerizable monomer oroligomer having a photopolymerizable group (e.g., a (meth)acryloylgroup, an acrylamide group and a vinyl group) [e.g., a monofunctionalphotopolymerizable compound such as a (meth)acrylic acid or a derivativethereof (e.g., a (meth)acrylate and a (meth)acrylamide), vinyl acetate,styrene and N-vinyl pyrrolidone; a polyfunctional (multifunctional)photopolymerizable compound such as a (meth)acrylate of polyol (e.g., anethylene glycol di(meth)acrylate, etc.); and the like] may be usedtogether.

[0152] As a photosensitizer in the negative resist, a conventionalphotosensitizer or photo-sensitizer may be employed, for example, anazide compound (e.g., an aromatic azide compound, especially an aromaticdiazide compound), a photoactive acid generator (e.g., an ester ofsulfonic acid, a salt of a Lewis acid, etc.) and a crosslinking agent(e.g., a melamine derivative such as a methylol melamine and aalkoxymethylmelamine, etc.), a pyrylium salt, a thiapyrylium salt, aphotodimerization sensitizer, a photopolymerization initiator [a ketone(acetophenone, propiophenone, an anthraquinone, a thioxanthone,benzophenone or a derivative thereof), a benzoin ether or a derivativethereof, an acylphosphineoxide, etc.], a dissolution inhibitor, and thelike.

[0153] The preferred negative resists include a combination of a resinhaving a phenolic hydroxyl group (e.g., a novolak resin and a polyvinylphenolic resin), a photoactive acid generator, and a crosslinking agent,and the like.

[0154] The typical base resin constituting a positive resist includes anovolak resin (e.g., a phenol novolak resin), a resin in which ahydrophilic group (e.g., a hydroxyl group and/or a carboxyl group) isprotected by a protective group capable of removing (removable) [e.g., apolyvinyl phenolic resin in which a phenolic hydroxyl group is protectedby a protective group capable of removing (removable) (e.g., ahomopolymer of a vinylphenol, or a copolymer of a vinylphenol and theabove-exemplified copolymerizable monomer, etc.), a hydroxyl and/orcarboxyl group-containing (meth)acrylic resin (e.g., a homo- orcopolymer of (meth)acrylate, or a copolymer of (meth)acrylate and theabove-exemplified copolymerizable monomer), a hydroxyl and/or carboxylgroup-containing cyclic olefinic resin, etc.] and the like.

[0155] The preferred base resin is a homo- or copolymer of a monomerforming a hydrophilic group (an alkali-soluble group or a group whichimparts alkali-solubility) by catalytic action of an acid (especially anacid generated from an acid generator), for example, a homo- orcopolymer of a vinyl-series monomer such as a polyvinyl phenolic resin;a homo- or copolymer of a vinyl-series or (meth)acrylic monomer having amonocyclic alicyclic hydrocarbon group, a homo- or copolymer of avinyl-series or (meth)acrylic monomer having a crosslinked cyclichydrocarbon group (such as a norbornyl group and an adamantyl group); ahomo- or copolymer of a cyclic olefin [e.g., a homopolymer of aC₅₋₈cyclic monoolefin such as cyclopentene, a crosslinked orterpene-series C₇₋₁₂cyclic monoolefin such as norbornene and bornene, acyclic diene such as cyclopentadiene and dicyclopentadiene or acopolymer with a copolymerizable monomer (e.g., the above-mentionedmonomers, besides maleic anhydride, etc.)]; and the like. In thesepolymers, the hydrophilic groups such as hydroxyl groups and carboxylgroups are usually protected by a protective group partially or wholly.The proportion of the protective group relative to the hydrophilic groupof the base resin may be about 10 to 100 mol %, preferably about 20 to100 mol %, and more preferably about 30 to 100 mol %.

[0156] Incidentally, the above-mentioned resin forming a hydrophilicgroup by deprotection may be obtained by polymerizing a monomer in whicha hydrophilic group is protected by a protective group (e.g., theprotective group exemplified in the section of the active alkoxide) inadvance, or may be obtained by polymerizing a monomer having ahydrophilic group and protecting the hydrophilic group of the obtainedresin by the protective group.

[0157] Among the monomers having a hydrophilic group, as a monomerhaving a hydroxyl group, such a polymerizable monomer having one orplural hydroxyl group(s) is mentioned, for example, a cyclic olefin(e.g., a monocyclic or a crosslinked cyclic olefin such as ahydroxycyclohexene and a hydroxynorbornene); a vinylphenolic monomer(e.g., a hydroxystyrene and a hydroxyvinyltoluene); ahydroxyalkyl(meth)acrylate (e.g., hydroxyC₂₋₄(meth)acrylate such ashydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate and2-hydroxybutyl(meth)acrylate, etc.); a vinyl monomer having a monocyclicalicyclic group such as a vinylhydroxycyclohexane, a (meth)acrylatehaving a monocyclic alicyclic group [e.g., ahydroxycycloalkyl(meth)acrylate (e.g., ahydroxycycloC₅₋₈alkyl(meth)acrylate, etc.) such as ahydroxyhexyl(meth)acrylate, a hydroxyoxacycloalkyl (meth)acrylate,etc.]; a (meth)acrylate having a crosslinked alicyclic group such as ahydroxynorbornyl(meth)acrylate and a hydroxyadamantyl(meth)acrylate(e.g., a hydroxybi- or tri-C₇₋₁₂cycloalkyl(meth)acrylate); a C₅₋₈cyclicmonoolefin such as a hydroxycyclopentene, a bridged cyclic orterpene-series C₇₋₁₂alkcyclic olefin such as a hydroxynorbornene and ahydroxybornene, a cyclic diene such as a hydroxycyclopentadiene and ahydroxydicyclopentadiene; and the like. These monomers having a hydroxylgroup can be used either singly or in combination.

[0158] As a monomer having a carboxyl group, there may be mentioned apolymerizable monomer having one or plural carboxyl group(s) or one orplural acid anhydride group(s), for example, a (meth)acrylic acid,maleic acid, fumaric acid, maleic anhydride, itaconic acid, avinylbenzoic acid, a (meth)acrylate having a monocyclic alicyclic groupsuch as a carboxycycloalkyl (meth)acrylate (e.g., acarboxycycloC₅₋₈alkyl(meth)acrylate; a (meth)acrylate having acrosslinked alicyclic group (e.g., a carboxybi- ortri-C₇₋₂₀cycloalkyl(meth)acrylate) such as acarboxynorbornyl(meth)acrylate and a carboxyadamantyl (meth)acrylate; aC₅₋₈cyclic monoolefin such as a carboxycyclopentene, a bridged cyclic orterpene-series C₇₋₁₂cyclic olefin such as a carboxynorbornene and acarboxybornene, a cyclic diene such as a carboxycyclopentadiene and acarboxydicyclopentadiene and the like. These monomers having a carboxylgroup can be used either singly or in combination.

[0159] These monomers having a hydrophilic group may be used in acombination of monomers having different kind of hydrophilic groups, forexample, a combination of a monomer having a hydroxyl group with amonomer having a carboxyl group. Further, a monomer having a hydrophilicgroup may be used in combination with a copolymerizable monomer.

[0160] As the copolymerizable monomer, there may be exemplified, forexample, an alkyl(meth)acrylate; a glycidyl(meth)acrylate; a styrenicmonomer such as styrene; a (meth)acrylate having a monocyclic alicyclicgroup such as a cycloalkyl(meth)acrylate and an oxacycloalkyl(meth)acrylate; a (meth)acrylate having a crosslinked alicyclic groupsuch as a norbornyl (meth)acrylate and an adamantyl (meth)acrylate. Thecopolymerizable monomer can be used either singly or in combination. Inthe copolymer with a copolymerizable monomer, the proportion of themonomer having a hydrophilic group is, relative to the total amount ofmonomers, about 10 to 100% by weight, preferably about 25 to 80% byweight, and more preferably about 30 to 70% by weight.

[0161] In the resin forming a hydrophilic group by deprotection, as aprotective group for the hydrophilic group, there may be mentioned theprotective groups exemplified in the section of the active metalalkoxide, for example, a protective group for a hydroxyl group such asan alkoxyalkyl group, an alkoxycarbonyl group, a cycloalkyl group, anoxacycloalkyl group and a crosslinked alicyclic group; and a protectivegroup for a carboxyl group such as an alkyl group.

[0162] The typical resin includes, for example, a resin (e.g., a vinylphenol, a homo- or copolymer of a hydroxyl group-containingalicyclic(meth)acrylate such as a hydroxycycloalkyl(meth)acrylate, ahydroxynorbornyl(meth)acrylate and a hydroxyadamantyl (meth)acrylate, ahomo- or copolymer of a cyclic olefin such as a hydroxynorbornene and ahydroxycyclopentadiene) in which a hydroxyl group is protected by aprotective group such as an alkoxyalkyl group, an alkoxycarbonyl group(t-BOC group, etc.) and an acetal group; a (meth)acrylic resin (e.g., ahomo- or copolymer of a hydroxyalkyl(meth)acrylate, etc.) in which ahydroxyl group is protected by an alicyclic group such as a cycloalkylgroup (including an oxacycloalkyl group and a bi- or tricycloalkyl groupsuch as norbornyl group and adamantyl group); a (meth)acrylic resin(e.g., a homo- or copolymer of an unsaturated carboxylic acid or an acidanhydride thereof such as (meth)acrylic acid and maleic anhydride, ahomo- or copolymer of a carboxyl group-containing alicyclic(meth)acrylate such as a carboxynorbornyl(meth)acrylate and acarboxyadamantyl(meth)acrylate, a homo- or copolymer of a cyclic olefinsuch as a carboxynorbornene and a carboxycyclopentadiene) in which acarboxyl group is protected by a protective group such as an alkyl group(e.g., t-butyl group).

[0163] The preferred positive resist includes a combination of a phenolnovolak resin and a photosensitizer (e.g., a quinonediazide such as adiazobenzoquinone derivative and a diazonaphthoquinone derivative,etc.), and a combination between a resin forming a hydrophilic group bya deprotection (especially deprotection by catalytic action of an acidgenerated from an acid generator) and a photosensitizer (photoactiveacid generator).

[0164] Further, the base resin may have various functional groups, forexample, a hydroxyl group, an alkoxy group, a carboxyl group, an acidanhydride group, an alkoxycarbonyl group, an acyl group and an aminogroup, in addition to the above-mentioned hydrophilic group.

[0165] As a photosensitizer in the positive resist, a conventionalphotosensitizer or photo-sensitizer may be selected from, for example, adiazonium salt (e.g., a diazonium salt, a tetrazonium salt, apolyazonium salt, etc.), a quinonediazide (e.g., a diazobenzoquinonederivative and a diazonaphthoquinone derivative), a photoactive acidgenerator and a dissolution inhibitor.

[0166] As the photoactive acid generator, there may be exemplified thefollowing compounds. Incidentally, trade names produced by Midori KagakuCo. Ltd. are written within parentheses for reference. As thephotoactive acid generator, there may be exemplified a derivative ofsulfonium salt [e.g., a sulfonic acid ester (an arylalkane sulfonate(particularly, a C₆₋₁₀arylC₁₋₂alkane sulfonate) such as1,2,3-tri(methylsulfonyloxy)benzene); an arylbenzene phosphonate(particularly, a C₆₋₁₀aryltoluene phosphonate which may have a benzoylgroup) such as 2,6-dinitrobenzyltoluene sulfonate and a benzointosylate; an aralkylbenzene sulfonate (particularly, aC₆₋₁₀aryl-C₁₋₄alkyltoluene sulfonate which may have a benzoyl group)such as 2-benzoyl-2-hydroxy-2-phenylethyltoluene sulfonate; a disulfonesuch as a diphenylsulfone; a Lewis acid salt (e.g., a triarylsulfoniumsalt (particularly, a triphenylsulfonium salt) such as atriphenylsulfonium hexafluorophosphate (TPS-102), a triphenylsulfoniumhexafluoroantimony (TPS-103), 4-(phenylthio)phenyldiphenylsulfoniumhexafluoroantimony (DTS-103), 4-methoxyphenyldiphenylsulfoniumhexafluoroantimony (MDS-103), a triphenylsulfonium methanesulfonyl, atriphenylsulfonium trifluoromethanesulfonyl (TPS-105) and atriphenylsulfonium nonafluorobutanesulfonyl (TPS-109), etc.], aderivative of phosphonium salt; a derivative of diarylhalonium salt[e.g., a Lewis acid salt such as a diaryliodonium salt (e.g.,diphenyliodoniumhexafluorophosphate, 4,4′-di(t-butylphenyl)iodoniumhexafluorophosphate (BBI-102), 4,4′-di(t-butylphenyl)iodoniumhexafluoroantimonate (BBI-103), 4,4′-di(t-butylphenyl)iodoniumtetrafluoroborate (BBI-101), 4,4′-di(t-butylphenyl)iodoniumtrifluoromethanesulfonate (BBI-105), 4,4′-di(t-butylphenyl)iodoniumcamphorsulfonate (BBI-106), diphehyliodonium trifluoromethanesulfonate(DPI-105), 4-methoxyphenyl phenyliodonium trifluoromethanesulfonate(DPI-105), etc.), etc.], a derivative of a diazonium salt (a Lewis acidsalt such as p-nitrophenyldiazoniumhexafluorophosphate), a diazomethanederivative, a triazine derivative [e.g., a haloalkyltriazinylaryl suchas 1-methoxy-4-(3,5-di(trichloromethyl)triazinyl)naphthalene (TAZ-106)and 1-methoxy-4-(3,5-di(trichloromethyl)triazinyl)benzene (TAZ-104), ahaloalkyltriazinylalkenylaryl such as1-methoxy-4-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene(TAZ-110),1,2-dimethoxy-4-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene(TAZ-113) and1-methoxy-2-[2-(3,5-ditrichloromethyltriazinyl)ethenyl]benzene(TAZ-118), etc.], an imidylsulfonate derivative[a succinimidylcamphorsulfonate (SI-106), succinimidyl phenylsulfonate (SI-100),succinimidyl toluylsulfonate (SI-101), succinimidyltrifluoromethylsulfonate (SI-105), phthalimidyl trifluorosulfonate(PI-105), naphthalimidyl camphorsulfonate (NAI-106), naphthalimidylmethanesulfonate (NAI-100), naphthalimidyl trifluoromethanesulfonate(NAI-105), naphthalimidyl toluylsulfonate (NAI-101), norborneneimidyltrifluoromethanesulfonate (NDI-105), etc.], and the like. Moreover,sulfone derivatives are also included, for example, a compound having aunit —SO₂—C(═N)— such as tradename “DAM-101”, “DAM-102”, “DAM-105” and“DAM-201”; a compound having a unit —CH₂—SO₂— such as “DSM-301”; acompound having a unit ═N—O—SO₂— such as “PAI-101”. Particularly, Lewisacid salts (e.g., Lewis acid salts such as phosphonium salts) arepreferred.

[0167] In the negative and positive resists, the amount to be used ofthe photosensitizer can be selected, for example, from the range ofabout 0.1 to 50 parts by weight, preferably about 1 to 30 parts byweight, and more preferably about 1 to 20 parts by weight (especiallyabout 1 to 10 parts by weight), relative to 100 parts by weight of abase resin.

[0168] Incidentally, the photosensitive resin (composition) can beselected according to exposing wavelength, too, for example, in the caseof using KrF excimer laser (248 nm) as a light source for exposure,there can be used, for example, a chemical-amplifying positivephotosensitive resin composition which comprises a vinyl-series resin(e.g., a polyvinyl phenol resin in which a hydroxyl group is protectedby a leaving group) or an acrylic polymer (e.g., a (meth)acrylic homo-or copolymer in which a carboxyl group is protected by a leaving group)and a photosensitizer (e.g., an acid generator), and a dissolutioninhibitor.

[0169] In the case of using ArF excimer laser (193 nm) as the lightsource for exposure, there can be used, for example, achemical-amplifying positive photosensitive resin composition whichcomprises a (meth)acrylic resin (e.g., an aliphatic group-containing(meth)acrylic homo- or copolymer in which a carboxyl group is protectedby a protective group (a leaving group) such as t-butyl group and analicyclic hydrocarbon group (e.g., an adamantyl group, etc.) or a resin(a homo- or copolymer) containing an alicyclic hydrocarbon such asnorbornene in the main chain, a photosensitizer (an acid generator), adissolution inhibitor, and the like.

[0170] Moreover, in the case of using F₂ excimer laser (157 nm) as alight source for exposure, there can be used, for example, achemical-amplifying positive photosensitive resin composition whichcomprises a polymer having a carbon-fluorine bond or a silicon-oxygenbond, or a homo- or copolymer of a phenolic monomer, a photosensitizer(an acid generator), a dissolution inhibitor, and the like.

[0171] In the photosensitive resin composition of the present invention,the amount of the active component can be selected from the wide rangeof about 0.01 to 1000 parts by weight as far as film-formability,sensitivity, resolution of patterns are not damaged, and is usuallyselected from the range of about 5 to 1000 parts by weight, preferablyabout 10 to 500 parts by weight and more preferably about 10 to 300parts by weight, especially about 10 to 100 parts by weight, on a solidmatter basis, relative to 100 parts by weight of a base resin.

[0172] To the photosensitive resin composition, various additives may beadded, for example, a stabilizer (e.g., an antioxidant), a plasticizer,a surfactant, a dissolution accelerator, and a coloring agent (e.g.,dyes, pigments), if necessary. Further, for ease of handling, forexample, in order to improve handling properties such as coating, thephotosensitive resin composition may comprise a solvent (e.g., thesolvents exemplified in the section of the active metal alkoxide).

[0173] The photosensitive resin composition of the present invention canbe prepared in accordance with a conventional method, for example, bymixing a photosensitive resin [a photosensitive resin compositioncomprising a base resin (a polymer or an oligomer) and aphotosensitizer] and an active component. The photosensitive resincomposition usually contains a solvent [e.g., the solvents exemplifiedin the section of the active metal alkoxide (e.g., a hydrophilic orwater-soluble solvent), for example, an ester of lactic acid such asethyl lactate; an alkylene glycol alkylether acetate such as ethyleneglycol alkylether acetate and propylene glycol methylether acetate(e.g., PGMEA); a (poly)oxyalkylene glycol alkylether acetate].

[0174] [Photosensitive Layer]

[0175] The photosensitive layer can be formed by applying (spreading orcoating) the above-described photosensitive resin composition to asubstrate (a base material). According to the intended pattern and use,the substrate can be suitably selected from metals (aluminum), glass,ceramics (e.g., alumina, copper doped alumina and tungsten silicate),plastics and others, and the substrate may be a semiconductor substratesuch as silicon wafer.

[0176] The surface of the substrate may be previously treated thereby toimprove the adhesion with the photosensitive layer, depending on itsintended use. The surface treatment includes a surface treatment usingthe silane coupling agent described above (e.g., a hydrolyticpolymerizable silane coupling agent having a polymerizable group) orothers, a coating treatment with an anchor coating agent or a base coatagent (e.g., a polyvinyl acetal, an acrylic resin, a vinylacetate-series resin, an epoxy resin, a urethane resin), or with amixture of such base coat agent with an inorganic fine particles(particles finely divided), and others.

[0177] Incidentally, after applying the photosensitive resin compositionto the substrate, solvents may be evaporated by drying. For example,removal of solvents may be conducted by soft-baking (pre-baking) withthe use of a heating means such as a hot plate.

[0178] So that the photosensitive resin composition of the presentinvention can improve plasma resistance (oxygen plasma resistance), heatresistance and dry etching resistance, too, it is preferred that thephotosensitive layer is formed at least on the surface of a resistlayer. The structure of the photosensitive layer can be selectedaccording to the process of forming patterns or the intended circuitstructures, and may be a single- or multi-layered structure (or alamination layer, a composite structure). For example, a single-layeredphotosensitive layer is utilized in a single-layer forming process inwhich a single photosensitive layer is formed on a substrate, andparticularly suitable for use in forming a heat-resistant pattern by dryetching. A multi-layered (composite structure) photosensitive layerimproves the oxygen plasma resistance largely, and thus it isadvantageous in improving the resolution even when the exposingwavelength (of light) for irradiation is at the vicinity of limit oflithography resolution. For example, a double-layered photosensitivelayer is utilized in a double-layer forming process comprising: formingan undercoat resist layer (which does not necessarily havephotosensitivity) on a substrate, forming a photosensitive layerthereon, exposing the photosensitive layer to light, developing thepattern, and etching the undercoat resist layer to give a pattern byplasma treatment (e.g., oxygen plasma treatment, etc.) or other means. Atriple-layered photosensitive layer can be utilized in a multi-layerforming process in which an undercoat layer, an intermediate layer and aphotosensitive layer are formed on a substrate in this order, exposed tolight and patterned by developing, and then the intermediate andundercoat layers are etched. The undercoat and intermediate layers maybe made from compositions composed of any photosensitive resins (e.g., aphotosensitive resin composition comprising a base resin and aphotosensitizer) and inorganic fine particles, or from photosensitiveresins containing no inorganic fine particle (e.g., a photosensitiveresin composition comprising a base resin and a photosensitizer).

[0179] The thickness of the photosensitive layer is not particularlyrestricted and, for example, can be selected within the range of about0.01 to 10 μm, preferably about 0.05 to 5 μm, preferably about 0.08 to 2μm, and is usually about 0.09 to 1 μm (e.g., about 0.1 to 0.7 μm).

[0180] The photosensitive layer can be formed by conventional coatingmethods such as spin coating method, dipping method, and casting method.If necessary, the coated composition is dried to remove the solventthereby to form a photosensitive layer.

[0181] [Process for Forming Pattern]

[0182] Patterns (particularly, minute patterns) can be carried out by aconventional lithography technique which is a combination of exposure,development and etching.

[0183] For example, a pattern can be formed by applying or coating thephotosensitive resin composition onto a substrate to form aphotosensitive layer, exposing the coating layer to light, anddeveloping the light-exposed layer. In particular, in the case using achemical-amplifying photosensitive resin, heating treatment ispreferably conducted after exposure (e.g., baking after exposure (postexposure bake, PEB)), to efficiently diffuse an acid generated byexposure. Moreover, after patterning by development, an etchingtreatment by plasma treatment (e.g., oxygen plasma) may be conducted.

[0184] The exposure of the photosensitive layer can be carried outaccording to a conventional method, for example, by pattern-irradiatingthe layer with light or pattern-exposing the layer to light, through agiven mask. As the light for patternwise exposure, various beams (e.g.,a beam of wavelengths of about 50 to 450 nm, especially about 100 to 450nm) are available, for example, a beam of a halogen lamp, a highpressure mercury lamp, a UV lamp and others; a radial ray (radiationray) of an excimer laser [e.g., XeCl (308 nm), KrF (248 nm), KrCl (222nm), ArF (193 nm), ArCl (172 nm) and F2 (157 nm)], an electron beam(g-ray (436 nm), i-ray (365 nm), etc.), X-ray and EB-ray, depending onthe photosensitive properties of the photosensitive resin composition,the degree of minuteness of the pattern, kinds of the base resin and soon, and the beams may be the ones of single-wavelength or complex(composite)-wavelength. In particular, the excimer lasers such as KrF(248 nm), ArF (193 nm) and F₂ (157 nm) are advantageously utilized.Moreover, with the use of resists comprising a non-aromatic base resin,transparency against shorter wavelength beams can be realized as well asimprovement of sensitivity. For example, in the case of using KrFexcimer laser (248 nm) as the light source for exposure, such achemical-amplifying photosensitive resin composition is available, forexample, a positive photosensitive resin composition which comprises aresin forming a hydrophilic group by deprotection [e.g., a polyvinylphenolic resin in which a hydroxyl group is protected by a protectivegroup or a (meth)acrylic resin in which a carboxyl group is protected bya protective group] and a photosensitizer (acid generator); and anegative photosensitive resin composition which comprises theabove-mentioned resin forming a hydrophilic group by deprotection, anacid generator and a crosslinking agent; and others.

[0185] Incidentally, the energy for exposure can be selected accordingto the photosensitive properties (e.g., solubility, etc.) of the abovephotosensitive resin composition, and the exposing time can be usuallyselected within the range of about 0.005 second to 10 minutes, andpreferably about 0.01 second to 1 minute.

[0186] After exposure, heat treatment may be conducted, if necessary. Inparticular, in the case of using a chemical-amplifying photosensitiveresin composition, heat treatment (PEB) is advantageously conducted. Thetemperature of heating (pre-bake and PEB) is about 50 to 150° C.,preferably about 60 to 150° C., more preferably about 70 to 150° C., andheating time is about 30 seconds to 5 minutes, preferably about 1 to 2minutes.

[0187] The high resolution pattern can be formed by developing thephotosensitive layer in a conventional manner after pattern-exposing.Various developers or developing agents (e.g., water, alkaline aqueoussolutions) are usable for development, and the choice thereof depends onthe type of the photosensitive resin composition. Preferred developersinclude water and alkaline developers. If necessary, the developer maycontain a small amount of an organic solvent (e.g., a hydrophilic orwater-soluble solvent such as alcohols typified by methanol, ethanol,and isopropanol, ketones typified by acetone, ethers typified bydioxanes and tetrahydrofurane, cellosolves, cellosolve acetates), asurfactant and others. There is no particular restriction on thedeveloping method, and the paddle (meniscus) method, dipping method,spraying method and others are adaptable.

[0188] Incidentally, besides the pre-bake and PEB, in an appropriatestep from application of the photosensitive resin composition todevelopment, the coated film (photosensitive layer) may be subjected toheat- or cure-treatment at a suitable temperature. If necessary, forexample, after the development, the coated film may be subjected toheat-treatment.

[0189] In the present invention, introduction of a functional groupwhich causes a difference in solubility by light exposure, into anactive component can achieve causing the difference in solubilitybetween exposed area and non-exposed area, even if the active componentis combined with a photosensitive resin (a photosensitive resincomposition comprising a base resin and a photosensitizer) to form aphotosensitive layer. In particular, when the group causing thedifference in solubility is a hydrophilic group protected by aprotective group, since the formed photosensitive layer is protected(especially becomes hydrophobic) and the surface of the layer becomeshydrophobic state, especially in a positive resist, hydrophobic state ina non-exposed area can be maintained, resulting in deprotecting of theprotecting group and accelerating dissolution in the exposed area. Thus,difference in dissolution rate between non-exposed area and exposed arealarger can be enlarged. Moreover improving edge roughness can berealized, as well as obtaining an edge being a sharp pattern in a planeshape and in a shape at cross section.

[0190] Incidentally, various hypotheses are proposed as a cause of theedge roughness, and part of the reason for the cause are said to be thefollowing factors, nonuniformity of resist composition in a pattern-edgepart, aggregation between a hydrophobic polymer (in the case of positivechemical-amplifying resist, a polymer before deprotection) and ahydrophilic polymer, nonuniform dispersal of a photoactive acidgenerator in a resist, and others.

INDUSTRIAL APPLICABILITY

[0191] According to the present invention, introduction of a group whichcauses a difference in solubility by light exposure, into an activecomponent can be enlarged the difference in solubility between exposedarea and non-exposed area, even if the active component is combined witha photosensitive resin (a photosensitive resin composition comprising abase resin and a photosensitizer) to form a photosensitive layer,resulting in forming a pattern with high sensitivity and highresolution. In particular, when an active component comprises a specificactive metal alkoxide or a polycondensate thereof, contamination ofimpurity can be efficiently inhibited (avoided). Further, according tothe photosensitive resin composition of the present invention, withkeeping etching resistance against oxygen plasma, edge roughness of thepattern can be largely improved, furthermore, high sensitivity for alight source of shorter wavelength light source can be achieved,resulting in improving resolution of patterns to a large extent.

[0192] Therefore, the present invention can be utilized in a variety ofapplication such as a material for forming circuits (a resist forsemiconductor production, a printed wiring board, etc.), a material forforming image (a printing plate material, a materials for reliefprinting, etc.). In particular, the present invention can beadvantageously utilized in the resist for semiconductor productionbecause high sensitivity and high resolution can be achieved.

EXAMPLES

[0193] Hereinafter, the present invention will be described in furtherdetail based on examples, and the examples should by no means beconstrued as defining the scope of the invention.

Examples 1 to 2 and Comparative Example 1

[0194] 1. Preparation of a Photosensitive Resin Composition

[0195] (1) Preparation of a Photosensitive Resin

[0196] To 1 part by weight of polyvinylphenol resin having a weightaverage molecular weight of 8,500 in which 37 mol % of the hydroxylgroup was substituted with t-BOC (tert-butoxycarbonyloxy) group, wasadded 0.02 part by weight of the photoactive acid generator representedby the following formula (A), and to the resultant mixture, 6 parts byweight of propylene glycol monomethyl ether acetate as a solvent wereadded and mixed to prepare a positive photoresist.

[0197] (2) Active Component (Silicasol)

[0198] (i) Synthesis of 1-(t-butoxycarbonyoxy)-4-iodobenzene

[0199] Into 1250 mL of acetone, were dissolved 125.0 g (568 mmol) ofp-iodophenol and 69 mg (5.7 mmol) of N,N-dimethylaminopyridine, and tothus obtained solution, 124 g (568 mmol) of di-t-butylcarbonate wasadded dropwise at 40° C. with stirring. After completion of dropping,the reaction solution was kept with stirring for one night to carry outthe reaction. After completion of the reaction, the obtained solutionwas put into 5 L of iced water. The formed precipitation was collectedby suction filtration, dried and recrystallized by methanol to provide113 g of 1-(t-butoxycarbonyoxy)-4-iodobenzene.

[0200] (ii) Synthesis of1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzene

[0201] Into a mixture of 1 L of triethylamine and 200 mL ofacetonitrile, were dissolved 55.0 g of1-(t-butoxycarbonyloxy)-4-iodobenzene synthesized in the step (i) and42.5 g of 3-trimethoxysilylpropyl acrylate, and the reaction system wassubstituted by argon by bubbling argon into liquid phase. To thereaction system, was added 770.0 mg of palladium acetate as a catalyst,the mixture was refluxed for one night (Hech reaction). After completionof the reaction, removing the solvent, a product was extracted by hexanefrom obtained residue. Hexane was removed from the extraction to prepare47.5 g of 3-(trimethyxysilyl)propylp-(t-butoxycarbonyloxy)cinnamate,that is,1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzenebeing the objective compound.

[0202] The formula of the reaction steps including the above-mentionedstep is shown as follows:

[0203] The ¹H-NMR and IR spectra of the obtained compound are shown inFIG. 1 and FIG. 2, respectively.

[0204]¹H-NMR(CDCl₃) ppm: 0.7(t, 2H, CH₂), 1.6(s, 9H, t-Bu), 1.8(q, 2H,CH₂), 3.6(s, 9H, OCH₃), 4.2(t, 2H, CH₂), 6.4(d, 1H, C═CH), 7.2(d, 2H,C₆H₄), 7.5(d, 2H, C₆H₄), 7.6(d, 1H, C═CH).

[0205] Moreover, in FIG. 2, absorption by C═O stretching vibration inester groups and carbonate groups was observed in the vicinity of 1700to 1800 cm⁻¹. It is obvious that the objective compound is obtained fromthese results.

[0206] (iii) Synthesis of a Silicasol

[0207] Into a 300 mL of reactor, were fed 70 g of propylene glycolmonomethylether acetate (PGMEA) and 54 g of 20% by weight aqueousammonia, and the mixture was stirred at 30° C. for 20 minutes. Into theresultant solution, 22.1 g of1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzenesynthesized in the step (ii), 2.34 g of tetraethoxysilane and 2.0 g oftriethoxymethylsilane were respectively added dropwise for 1 hour, andfurther stirred at 30° C. for 6 hours. Thereafter, the reaction solutionwas filtered by a membrane filter having a mean hole size of 0.1 μm, andthen ammonia was removed by rinsing the filtrate with purified water,and further water was removed by dehydration under a reduced pressure.After that, the content of propylene glycol monomethylether acetate(PGMEA) was adjusted by addition, or removal under a reduced pressure toprepare a propylene glycol monomethylether acetate (PGMEA) solution ofsilicasol in which the content of silicasol is 30% by weight.

[0208] (3) Preparation of a Photosensitive Resin Composition

[0209] The photosensitive resin obtained in the step (1) and the activecomponent (silicasol) obtained in the step (2) were mixed together inthe ratio shown in Table 1 (denoted by solid ratio without solvent) toprepare a photosensitive resin composition. Incidentally, the examplewithout the active component (silicasol) was made as Comparative Example1.

[0210] 2. Pattern Formation and Evaluation of Properties (Sensitivity,Resolution and Oxygen Plasma Resistance)

[0211] (1)Pattern Formation

[0212] After treating a washed silicon wafer by hexamethyldisilazane,the photosensitive resin composition was coated on the wafer by means ofa spin coater in order that a resist layer of 0.4 μm thick after driedwas formed and the wafer was baked on a hot plate at 100° C. for 1minute. Thereafter, exposure was conducted through a test mask having aline-and-space pattern with different line widths, using a reducedprojection exposing machine (manufactured by Canon Inc., FPA-3000EX5,NA=0.63) having an exposing wavelength of 248 nm (KrF excimer laser)with the exposure amount varied in steps. After baking the wafer at 100°C. on a hot plate for 1 minute, the wafer was paddle-developed with2.38% by weight a tetramethylammonium hydroxide aqueous solution for 1minute to give a positive pattern.

[0213] (2) Evaluation of the Properties

[0214] The positive pattern was evaluated for its properties accordingto the following manner.

[0215] (i) Sensitivity: expressed in terms of such an amount of exposeddose to print just as the same size of the mask with a line width of0.25 μm that the ratio of the width of the line relative to that of thespace becomes 1:1 (the smaller the value is, the higher the sensitivityis).

[0216] (ii) Resolution: expressed in terms of a minimum width of thelines distinctly formed by exposing at the amount of exposed dose inwhich the line width of the mask is 0.25 μm, the ratio of the width ofthe line relative to that of the space becomes 1:1 (the smaller thevalue is, the higher the resolution is).

[0217] (iii) Oxygen plasma resistance: using a plasma etching device(manufactured by Tokyo Shinku, K.K., SUPER COAT N400), the wafers afterdevelopment were subjected to oxygen plasma etching under the followingconditions.

[0218] Feeding system: cathode couple

[0219] Electrode size: 80 mmØ

[0220] Gas: oxygen

[0221] Pressure: 8.645 Pa

[0222] rf voltage applied: 85W

[0223] rf electric power density: 1.69 W/cm²

[0224] Treatment time: 5 minutes

[0225] The film thickness of each wafer after etching was measured. Thethickness of the lost portion by etching was divided by etching time togive a value represented by the rate of oxygen plasma (O₂-RIE rate,nm/sec). The smaller the value is, the higher the oxygen plasmaresistance is. The results are shown in Table 1. TABLE 1 CompositionActive Photosensitive component resin (silicasol) O₂-RIE (parts by(parts by Sensitivity Resolution rate weight) weight) (mJ/cm²) (μm)(nm/sec) Ex. 1 1 0.11 30 0.17 45 Ex. 2 1 0.25 25 0.17 20 Comp. 1 0 500.23 70 Ex. 1

[0226] Into methylisobutylketone, were dissolved 2-methyladamantylmethacrylate and γ-butylolactone methacrylate at the nurture ratio(molar ratio) of 1/1, radical polymerization was conducted at 80° C. for10 hours using azobisisobutylonitrile (AIBN) as an initiator to preparea resin having a weight average molecular weight of 14,500. n-Hexane wasused as a solvent for reprecipitation. Into 1 part by weight of theobtained resin, was added 0.02 part by weight of the photoactive acidgenerator represented by the following formula (B), and mixed with 7parts by weight of propylene glycol monomethyl ether acetate as asolvent to prepare a positive photoresist.

[0227] (2) Active Component (Silicasol)

[0228] (i) Synthesis of tert-butyl3-[3-(trimethoxysilyl)propylthio]Propionate

[0229] Into 300 mL of dehydrated ethyl acetate, were dissolved 58.8 g(0.3 mol) of 3-(trimethoxysilyl)-1-propanethiol and 38.4 g (0.3 mol) oftert-butyl acrylate, and the reaction system was substituted by argon bybubbling argon in thus obtained solution. To the reaction solution, wasadded 2.94 g of dicumylperoxide (manufactured by NOF Corporation ltd.,PERBUTYL PV) as a radical initiator, the mixture was refluxed withheating for 24 hours. After completion of the reaction, solvent wasremoved to prepare 96.0 g (0.294 mol) of tert-butyl3-[3-(trimethoxysilyl)propylthio]propionate being the objectivecompound.

[0230] The formula of the reaction steps is shown as follows:

[0231] The ¹H-NMR and IR spectra of the obtained compound are shown inFIG. 3 and FIG. 4, respectively.

[0232]¹H-NMR: 0.7, 1.6-1.8, and 2.4-2.8 ppm: methylene(CH₂)

[0233] 1.4 ppm: t-butyl(CH₃)₃C

[0234] 3.6 ppm: methoxy(OCH₃)₃

[0235] Moreover, in FIG. 4, specific absorption by carbonyl group wasobserved in the vicinity of 1730 to 1740 cm⁻¹. It is obvious thatobjective compound is obtained from these results.

[0236] (ii) Synthesis of a Silicasol

[0237] Into a 300 ml reactor, were fed 70 g of propylene glycolmonomethylether acetate (PGMEA) and 54 g of 20% by weight aqueousammonia, and the reaction mixture was stirred at 30° C. for 20 minutes.Into the resultant mixture, 42.0 g of tert-butyl3-[3-(trimethoxysilyl)propylthio]propionate synthesized in the step (i),3.1 g of tetraethoxysilane and 2.7 g of triethoxymethylsilane wererespectively added dropwise for 1 hour, and further stirred at 30° C.for 6 hours. Thereafter, the reaction solution was filtered by amembrane filter having mean hole size of 0.1 μm, and then ammonia wasremoved by rinsing the filtrate with purified water, and further waterwas removed by dehydration under a reduced pressure. After that, thecontent of propylene glycol monomethylether acetate (PGMEA) was adjustedby addition or removal under a reduced pressure to prepare a propyleneglycol monomethylether acetate (PGMEA) solution of silicasol in whichcontent of silicasol is 30% by weight.

[0238] (3) Preparation of a Photosensitive Resin Composition

[0239] The photosensitive resin obtained in the step (1) and the activecomponent (silicasol) obtained in the step (2) were mixed together inthe ratio shown in Table 2 (denoted by solid ratio without solvent) toprepare a photosensitive resin composition. Incidentally, the examplewithout the active component (silicasol) was made as ComparativeExample.

[0240] 2. Pattern Formation and Evaluation of Properties (Sensitivity,Resolution and Oxygen Plasma Resistance)

[0241] (1)Pattern Formation

[0242] After treating a washed silicon wafer by hexamethyldisilazane,the photosensitive resin composition was coated on the wafer by means ofa spin coater in order that a resist layer of 0.3 μm thick after driedwas formed, and the wafer was baked on a hot plate at 130° C. for 1minute. Thereafter, exposure was carried out through a test mask havinga line-and-space pattern with different line widths, using a reducedprojection exposing machine (NA=0.63) having an exposing wavelength of193 nm (ArF excimer laser) with the exposure amount varied in steps.After baking the wafer at 130° C. on a hot plate for 1 minute, the waferwas paddle-developed with 2.38% by weight a tetramethylammoniumhydroxide aqueous solution for 1 minute to give a positive pattern.

[0243] (2) Evaluation of Properties of Resist

[0244] The positive pattern was evaluated for its properties accordingto the following manner.

[0245] (i) Sensitivity: expressed in terms of such an amount of exposeddose to print just as the same size of the mask with a line width of0.20 μm that the ratio of the width of the line relative to that of thespace becomes 1:1 (the smaller the value is, the higher the sensitivityis).

[0246] (ii) Resolution: expressed in terms of a minimum width of thelines distinctly formed by exposing at the amount of exposed dose inwhich the line width of the mask is 0.20 μm, the ratio of the width ofthe line relative to that of the space becomes 1:1 (the smaller thevalue is, the higher the resolution is).

[0247] (iii) Oxygen plasma resistance: evaluated in the same manner asExample 1.

[0248] The results are shown in Table 2. TABLE 2 Composition ActivePhotosensitive component resin (silicasol) O₂-RIE (parts by (parts bySensitivity Resolution rate weight) weight) (mJ/cm²) (μm) (nm/sec) Ex. 31 0.11 21 0.15 55 Ex. 4 1 0.25 15 0.14 25 Comp. 1 0 30 0.19 90 Ex. 2

Examples 5 to 8 and Comparative Example 3

[0249] 1. Preparation of a Photosensitive Resin Composition

[0250] (1) Preparation of Photosensitive Resin

[0251] Into 200 mL of toluene, were dissolved 30 g of tert-butylmethacrylate and 0.2 g of azobisisobutylonitrile. The reactor issubstituted by argon, polymerization was conducted, by heating solutionat 60° C. for 12 hours with stirring. After completion of thepolymerization, the reaction solution was poured into a large amount ofmethanol to solidify a resin, and the solidified resin was rinsed withmethanol several times. This resin was dried at room temperature, undera reduced pressure for one night to prepare a poly tert-butylmethacrylate having a weight average molecular weight of 35000 at ayield of 33%.

[0252] Into 1 part by weight of this poly tert-butyl methacrylate, wasadded 0.02 part by weight of the photoactive acid generator (B) used inExample 3, and mixed with 6 parts by weight of propylene glycolmonomethyl ether acetate as a solvent to prepare a positive photoresist.

[0253] (2) Active Component (Silicasol)

[0254] (i) Synthesis of a Silicasol

[0255] Into a 300 ml reactor, were fed 70 g of propylene glycolmonomethylether acetate (PGMEA) and 54 g of 20% by weight aqueousammonia, and the reaction mixture was stirred at 30° C. for 20 minutes.Into the resultant solution, 26.3 g of tert-butyl3-[3-(triethoxysilyl)propylthio]propionate synthesized in the step(2)(ii) in Example 3, 7.8 g of tetraethoxysilane and 6.7 g oftriethoxymethylsilane were respectively added dropwise for 1 hour, andfurther stirred at 30° C. for 6 hours. Thereafter, the reaction solutionwas filtered by a membrane filter having mean hole size of 0.1 μm, andthen ammonia was removed by rinsing the filtrate with purified water,and further water was removed by dehydration under a reduced pressure.After that, the content of propylene glycol monomethylether acetate(PGMEA) was adjusted to prepare a propylene glycol monomethyletheracetate (PGMEA) solution of silicasol in which content of silicasol is30% by weight.

[0256] (3) Preparation of a Photosensitive Resin Composition

[0257] The photosensitive resin obtained in the step (1) and the activecomponent (silicasol) obtained in the step (2) were mixed together inthe ratio specified in Table 3 (denoted by solid ratio without solvent)to prepare a photosensitive resin composition. Incidentally, the examplewithout the active component (silicasol) was made as Comparative Example3.

[0258] 2. Pattern Formation and Evaluation of Properties (Sensitivity,Resolution and Oxygen Plasma Resistance)

[0259] (1)Pattern Formation

[0260] After treating a washed silicon wafer by hexamethyldisilazane,the photosensitive resin composition was coated on the wafer by means ofa spin coater in order that a resist layer of 0.12 μm thick after driedwas formed, and the wafer was baked on a hot plate at 130° C. for 1minute. Thereafter, exposure was carried out using an exposing machine(manufactured by Litho Tech Japan Co. Ltd., VUVES-1200) having anexposing wavelength of 157 nm (F₂ excimer laser) with the exposureamount varied in steps. After baking the wafer at 130° C. on a hot platefor 1 minute, the wafer was paddle-developed with 2.38% by weight of atetramethylammonium hydroxide aqueous solution for 1 minute to give apositive pattern.

[0261] (2) Evaluation of the Properties

[0262] The positive pattern was evaluated for its properties accordingto the following manner.

[0263] (i) Sensitivity: expressed in terms of the minimum amount oflight exposure in which a resist was completely dissolved (the smallerthe value is, the higher the sensitivity is).

[0264] (ii) Resolution: plotting logarithm of dissolving rate (nm/sec)relative to the amount of light exposure, finding slope angle θ of theliner part, making the γ value of tan θ as index of resolution(generally the larger the γ value is, the higher the resolution is).

[0265] (iii) Oxygen plasma resistance: evaluated in the same manner asExample 1.

[0266] The results are shown in Table 3. TABLE 3 Composition ActivePhotosensitive component resin (silicasol) O₂-RIE (parts by (parts bySensitivity Resolution rate weight) weight) (mJ/cm²) (γ value) (nm/sec)Ex. 5 1 0.11 5 3.8 93 Ex. 6 1 0.25 4 5.3 48 Ex. 7 1 0.43 3 4.3 32 Ex. 81 1.00 1.5 3.0 20 Comp. 1 0 8 1.2 150 Ex. 3

Examples 9 to 12 and Comparative Example 4

[0267] 1. Photosensitive Resin Composition

[0268] (1) Preparation of a Photosensitive Resin

[0269] To 1 part by weight of polyvinylphenol resin having a weightaverage molecular weight of 8,000 in which 35 mol % of the hydroxylgroup was substituted with t-BOC (tert-butoxycarbonyloxy) group, wasadded 0.02 part by weight of the photoactive acid generator representedby the following formula (A), and to the resultant mixture, 6 parts byweight of propylene glycol monomethyl ether acetate as a solvent wereadded and mixed to prepare a positive photoresist.

[0270] (2) Active Component

[0271] (i) (ii) Synthesis of 1-(t-butoxycarbonyloxy)-4-iodobenzene and1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzene

[0272] In the same manner with the steps (i) and (ii) in Example 1,1-(t-butoxycarbonyloxy)-4-iodobenzene and1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzenewere synthesized.

[0273] (iii) Modification of Silicasol

[0274] 0.45 g of1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzeneobtained by the step (ii) was mixed with 15 g of colloidal silica(manufactured by Nissan Chemical Industries, Ltd., NPC-ST, silicasolcontent: 30%by weight) and 0.23 g of 0.05 mol/L hydrochloric acid,stirred at room temperature for 16 hours to modify silicasol. In thisexample, a weight ratio of 3-(trimethoxysilyl)propylp-(t-butoxycarbonyloxy)cinnamate relative to silicasol is 1-10, andexpressed it as a modified amount of 10% (modified silicasol A).

[0275] Moreover, in the modifying step of the silicasol, modifiedsilicasols were prepared wherein the modified amount by3-(trimethoxysilyl)propyl p-(t-butoxycarbonyloxy)cinnamate is 15%(modified silicasol B) and 30% (modified silicasol C), respectively, inthe same operation with the above, except for the weight ratio of1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzene/colloidalsilica NPC-ST (solid basis)/hydrochloric acid (concentration of 0.05mol/L) is 1.5/10/0.75 and 3/10/1.5.

[0276] (3) Preparation of a Photosensitive Resin Composition

[0277] The photosensitive resin obtained in the step (1) and themodified silicasol obtained in the step (2) were mixed together in theratio specified in Table 4 (denoted by solid ratio without solvent) toprepare a photosensitive resin composition. Incidentally, the examplewithout the modified silicasol was made as Comparative Example 4.

[0278] 2. Pattern Formation and Evaluation of Properties (Sensitivity,Resolution and Oxygen Plasma Resistance)

[0279] (1)Pattern Formation

[0280] The photosensitive resin composition was coated on a washedsilicon wafer by means of a spin coater in order that a resist layer of0.40 μm thick after dried was formed, and the wafer was baked on a hotplate at 100° C. for 1 minute. Thereafter, exposure was carried outthrough a test mask having a line-and-space pattern with different linewidths, using a reduced projection exposing machine (manufactured byCanon Inc., FPA-3000EX5, NA=0.63) having an exposing wavelength of 248nm with the exposure amount varied in steps. After baking the wafer at100° C. on a hot plate for 1 minute, the wafer was paddle-developed with2.38% by weight of a tetramethylammonium hydroxide aqueous solution for1 minute to give a positive pattern.

[0281] (2) Evaluation of the Properties

[0282] The positive pattern was evaluated for its properties accordingto the following manner.

[0283] (i) sensitivity: evaluated in the same manner as Example 1.

[0284] (ii) resolution: evaluated in the same manner as Example 1.

[0285] (iii) heat resistance: the wafers after development wereseparately placed on hot plates different in temperature for 5 minutes.The temperatures at which the patterns with 500 μm width began to deformwere used as indexes of heat resistance.

[0286] (iv) Oxygen plasma resistance: evaluated in the same manner asExample 1.

[0287] The results are shown in Table 4. TABLE 4 Composition ModifiedModified Photosensitive colloidal amount of resin silica colloidal Heat(parts by (parts by silica Sensitivity Resolution resistance O₂-RIE rateweight) weight) (%) (mJ/cm²) (μm) (° C.) (nm/sec) Ex. 9 1 A 10 25 0.17120 41 0.11 Ex. 10 1 A 10 20 0.18 130 11 0.25 Ex. 11 1 B 15 25 0.16 12040 0.11 Ex. 12 1 C 30 28 0.15 120 42 0.11 Comp. Ex. 4 1 0 — 50 0.23 10070

Example 13 and Comparative Examples 5 to 6

[0288] 1. Preparation of a Photosensitive Resin Composition

[0289] (1) Preparation of a Photosensitive Resin

[0290] Into a reactor, were fed 30 g of t-butyl methacrylate and 0.2 gof azobisisobutylonitrile, and dissolved to 200 mL of toluene. Thereactor is substituted by argon, polymerization was conducted by heatingsolution at 60° C. with stirring for 12 hours. After completion of thepolymerization, the reaction solution was poured into a large amount ofmethanol to solidify a resin. The solidified resin was rinsed withmethanol several times. Thus obtained resin was dried at roomtemperature, under a reduced pressure for one night to prepare a polytert-butyl methacrylate having a weight average molecular weight of35000 (33% yield).

[0291] Into 1 part by weight of thus obtained poly tert-butylmethacrylate resin, was added 0.02 part by weight of the photoactiveacid generator represented by the following formula (B), and mixed with6 parts by weight of propylene glycol monomethyl ether acetate as asolvent to prepare a positive photoresist.

[0292] (2) Active Component

[0293] (i) Synthesis of tert-butyl3-[3-(triethoxysilyl)propiothio]propionate

[0294] tert-Butyl 3-[3-(triethoxysilyl)propiothio]propionate wassynthesized in the same manner as the step (i) in Example 3.

[0295] (ii) Modification of Silicasol

[0296] 0.45 g of tert-butyl 3-[3-(triethoxysilyl)propiothio]propionatesynthesized by the step (i) was mixed with 15 g of colloidal silica(manufactured by Nissan Chemical Industries, Ltd., NPC-ST, silicasolcontent: 30% by weight) and 0.23 g of 0.05 mol/L hydrochloric acid, andstirred at room temperature for 16 hours to modify silicasol. In thisexample, the modified amount was 10% (modified silicasol D).

[0297] (3) Preparation of a Photosensitive Resin Composition

[0298] The photosensitive resin obtained in the step (1) and themodified silicasol D obtained in the step (2) were mixed together in theratio specified in Table 5 (denoted by solid ratio without solvent) toprepare a photosensitive resin composition. Incidentally, the exampleusing unmodified silicasol [manufactured by Nissan Chemical Industries,Ltd., colloidal silica NPC-ST, silicasol content: 30% by weight] insteadof the modified silica D was made as Comparative Example 5, and theexample without the silicasol was made as Comparative Example 6.

[0299] 2. Pattern Formation and Evaluation of Properties (Sensitivity,Resolution, Heat Resistance and Oxygen Plasma Resistance)

[0300] (1) Pattern Formation

[0301] The photosensitive resin composition was coated on a washedsilicon wafer by means of a spin coater in order that a resist layer of0.30 μm thick after dried was formed, and the wafer was baked on a hotplate at 130° C. for 1 minute. Thereafter, exposure was carried outthrough a test mask having a line-and-space pattern with different linewidths, using a reduced projection exposing machine (NA=0.60) having anexposing wavelength of 193 nm with the exposure amount varied in steps.After baking the wafer at 130° C. on a hot plate for 1 minute, the waferwas paddle-developed with 2.38% by weight of a tetramethylammoniumhydroxide aqueous solution for 1 minute to give a positive pattern.

[0302] (2) Evaluation of the Properties

[0303] The positive pattern was evaluated for its properties accordingto the following manner.

[0304] (i) sensitivity, (ii) resolution and (iii) oxygen plasmaresistance: evaluated in the same manner as Example 3. The results areshown in Table 5. TABLE 5 Composition Modified Modified Photosensitivecolloidal amount of resin silica colloidal (parts by (parts by silicaSensitivity Resolution O₂-RIE rate weight) weight) (%) (mJ/cm²) (μm)(nm/sec) Ex. 13 1 modified 10 7 0.14 68 silicasol D 0.11 Comp. Ex. 5 1un- 0 7 0.18 72 modified silicasol 0.11 Comp. Ex. 6 1 0 — 14 0.18 150

Examples 14 to 16 and Comparative Examples 7 to 8

[0305] 1. Preparation of a Photosensitive Resin Composition

[0306] The photosensitive resin (1) used in Example 9 or thephotosensitive resin (2) used in Example 13, and a modified silicasolwere mixed together in the ratio specified in Table 3 (denoted by solidratio without solvent) to prepare a photosensitive resin composition.

[0307] Incidentally, regarding Example 15, in the modification step ofsilicasol in Example 9, a modified silicasol of 100% modification amount(modified silicasol E) was used, which was obtained by the same manneras Example 9 except that the weight ratio of1-[2-{(3-trimethoxysilyl)propyloxycarbonyl}vinyl]-4-(t-butoxycarbonyloxy)benzene/colloidalsilica NPC-ST (solid basis)/hydrochloric acid (concentration of 0.5mol/L) was used as 10/10/5.

[0308] 2. Pattern Formation and Evaluation of Properties (Sensitivity,Resolution, Heat Resistance and Oxygen Plasma Resistance)

[0309] (1) Pattern Formation

[0310] The photosensitive resin composition was coated on a washed waferby means of a spin coater in order that a resist layer of 0.12 μm thickafter dried was formed, and the wafer was baked on a hot plate at thetemperature shown in Table 3 for 1 minute. Thereafter, exposure wascarried out through a test mask having a line-and-space pattern withdifferent line widths, using an exposing machine (manufactured by LithoTech Japan Co. Ltd., VUVES-4500) having a F₂ excimer laser (exposingwavelength: 157 nm) as an exposure light source with the exposure amountvaried in steps. After baking the wafer at the temperature shown inTable 3 on a hot plate for 1 minute, the wafer was paddle-developed with2.38% by weight of a tetramethylammonium hydroxide aqueous solution for1 minute to give a positive pattern.

[0311] (2) Evaluation of the Properties

[0312] Regarding the positive pattern, (i) sensitivity was expressed asthe light exposure in which film thickness of the exposed area becomes0, (the smaller the value is, the higher the sensitivity is), (ii)resolution was evaluated with the following process, making asensitivity curve plotting of the thickness of a residual resist layerin the exposed area, relative to logarithm of an amount of lightexposure, and finding a slope of the linear part (γ value) at the pointof film thickness being 0 to treat it as index of resolution (the largerthe value is, the higher the resolution is). Moreover, (iii) oxygenplasma resistance: evaluated in the same manner as Example 1.

[0313] The results are shown in Table 6. TABLE 6 Composition ModifiedModified Photosensitive colloidal amount of Baking resin silicacolloidal after (parts by (parts by silica Pre baking exposureSensitivity O₂-RIE rate weight) weight) (%) (° C.) (° C.) (mJ/cm²) γvalue (nm/sec) Ex. 14 resin(1) A 10 100 100 16 3.7 39 1 0.11 Ex. 15resin(1) E 100 100 100 12 4.5 37 1 0.11 Comp. resin(1) 0 — 100 100 351.2 70 Ex. 7 1 Ex. 16 resin(2) D 10 130 130 9 4.2 20 1 0.25 Comp.resin(2) 0 — 130 130 15 1.5 150 Ex. 8 1

Examples 17 to 20 and Comparative Examples 9 to 11

[0314] 1. Preparation of a Photosensitive Resin Composition

[0315] (1) Photosensitive Resin

[0316] To 1 part by weight of polyvinylphenol resin having a weightaverage molecular weight of 8,500 in which 45 mol % of the hydroxylgroup was substituted with ethoxyethyl group, was added 0.03 part byweight of the photoactive acid generator represented by theabove-mentioned formula (A), and to the resultant mixture, 6 parts byweight of propylene glycol monomethyl ether acetate as a solvent wereadded and mixed to prepare a positive photoresist.

[0317] (2) Active Component

[0318] (i) Synthesis of 1-(t-butoxycarbonyoxy)-4-bromobenzene

[0319] Into 200 ml of acetone, in which 25.0g (144.5 mmol) ofp-bromophenol and 17.7 mg (0.14 mmol) of N,N-dimethylaminopyridine weredissolved, 31.5 g (144.5 mmol) of di-t-butylcarbonate was added dropwiseat 40° C. After dropping, the reaction was kept with stirring for onenight. After completion of the reaction, the reaction solution was putinto 1 L of iced water. The formed precipitation was collected bysuction filtration, dried and recrystallized by methanol to prepare 22.6g of 1-(t-butoxycarbonyloxy)-4-bromobenzene.

[0320] (ii) Synthesis of1-(2-trimethoxysilylvinyl)-4-(t-butoxycarbonyloxy)benzene

[0321] Into a mixture of 20 ml of triethylamine and 40 ml ofacetonitrile, were dissolved 15.0 g (54.9 mmol) of1-(t-butoxycarbonyloxy)-4-bromobenzene synthesized in the step (i) and9.76 g (65.9 mmol) of vinyltrimethoxysilane, and the reaction system wassubstituted by argon by bubbling argon in thus obtained solution. In thereaction system, was added 246.5 mg (1.1 mmol) of palladium acetate as acatalyst, the mixture was refluxed for one night. After completion ofthe reaction, solvent was removed, and the obtained residue wasextracted by hexane. Hexane was removed from the extraction to prepare9.5 g of 1-(2-trimethoxysilylvinyl)-4-(t-butoxycarbonyloxy)benzene beingthe objective compound.

[0322] The formula of the above-mentioned reaction steps is shown asfollows:

[0323] The ¹H-NMR spectrum of the obtained compound is shown in FIG. 5.

[0324]¹H-NMR(CDCl₃) ppm: 1.6(s, 9H, t-Bu), 3.6(s, 9H, OCH₃), 6.1(d, 1H,C═CH), 7.2(d, 2H, C₆H₄), 7.3(d, 1H, C═CH), 7.5(d, 2H, C₆H₄)

[0325] (ii) Modification of Silicasol

[0326] 1-(2-Trimethoxysilylvinyl)-4-(t-butoxycarbonyloxy)benzeneobtained in the step (ii) was mixed with colloidal silica (manufacturedby Nissan Chemical Industries, Ltd., NPC-ST, silicasol content: 30% byweight) and 0.05 mol/L hydrochloric acid, in a weight ratio of1-(2-trimethoxysilylvinyl)-4-(t-butoxycarbonyloxy)benzene/colloidalsilica NPC-ST (without solvent)/hydrochloric acid being 5/10/2.5(modified amount of 50%) and 10/10/5 (modified amount of 100%), themixture was stirred at room temperature for 16 hours to modify silicasol(the former is named as modified silicasol F, the latter, silicasol G).

[0327] (3) Preparation of a Photosensitive Resin Composition

[0328] The photosensitive resin obtained in the step (1) and themodified silicasol obtained in the step (2) were mixed together in theratio shown in Table 7 (denoted by solid ratio without solvent) toprepare a photosensitive resin composition. Incidentally, the examplesusing the unmodified silicasol instead of the modified silicasol weremade as Comparative Example 9 and 10, and the example without thesilicasol was made as Comparative Example 11.

[0329] 2. Pattern Formation and Evaluation of the Properties(Sensitivity, Resolution and Oxygen Plasma Resistance)

[0330] Conducted in the same way as Example 9. TABLE 7 CompositionModified Modified colloidal amount of Photosensitive silica colloidalresin (parts (parts by silica Sensitivity Resolution O₂-RIE rate byweight) weight) (%) (mJ/cm²) (μm) (nm/sec) Ex. 17 1 modified 50 28 0.1633 silicasol F 0.11 Ex. 18 1 modified 50 20 0.15 8 silicasol F 0.25 Ex.19 1 modified 100 30 0.15 32 silicasol G 0.11 Ex. 20 1 modified 100 190.14 8 silicasol G 0.25 Comp. Ex. 1 un- 0 28 0.21 35 9 modifiedsilicasol 0.11 Comp. Ex. 1 un- 0 21 0.23 10 10 modified silicasol 0.25Comp. Ex. 1 0 — 40 0.21 75 11

Examples 21 to 23 and Comparative Example 12

[0331] 1. Preparation of a Photosensitive Resin Composition

[0332] (1) Photosensitive Resin

[0333] To 1 part by weight of polyvinylphenol resin having a weightaverage molecular weight of 9,300 in which 40 mol % of the hydroxylgroup was substituted with ethoxyethyl group, was added 0.02 part byweight of the photoactive acid generator represented by theabove-mentioned formula (A), and to the resultant mixture, 6 parts byweight of propylene glycol monomethyl ether acetate as a solvent wereadded and mixed to prepare a positive photoresist.

[0334] (2) Active Component

[0335] (i) Synthesis of 1-benzyloxy-4-t-butoxycarbonyoxybenzene

[0336] Into 200 ml of acetone, were dissolved 25.0g (124.9 mmol) of4-benzyloxyphenol and 15.3 mg (0.12 mmol) of N,N-dimethylaminopyridine,and 27.2 g (124.9 mmol) of di-t-butylcarbonate was added dropwise at 40°C. After completion of dropping, the reaction was kept with stirring forone night. After completion of the reaction, the reaction solution wasput into 1 L of iced water. The formed precipitation was collected bysuction filtration, dried, and recrystallized by methanol to prepare22.8 g of 1-benzyloxy-4-t-butoxycarbonyoxybenzene.

[0337] (ii) Synthesis of 4-t-butoxycarbonyoxyphenol

[0338] Into 20.0 g (66.6 mmol) of1-benzyloxy-4-t-butoxycarbonyoxybenzene synthesized in the step (i),were fed 150 ml of ethanol and 0.5 g of 10%-palladium carbon powder, andthe mixture was reacted with 1492.2 ml (66.6 mmol) of hydrogen at roomtemperature with stirring. The reaction solution was filtrated to removepalladium carbon powder, and the filtrate was concentrated. Afterredissolving the concentrated filtrate to toluene, the solution wasfiltrated to remove insoluble. And then, the solution was kept still,and recrystallized to prepare 4-t-butoxycarbonyoxyphenol.

[0339] (iii) Reaction of 4-t-butoxycarbonyoxyphenol with Silane CouplingAgent

[0340] Into 8.4 g (40.0 mmol) of 4-t-butoxycarbonyoxyphenol synthesizedin the step (ii), were fed 20 ml of n-hexane dehydrated sufficiently,and 9.9 g (40.0 mmol) of 3-isocyanatopropyltriethoxysilane, and themixture was allowed to react at room temperature for 16 hours withstirring.

[0341] The reaction solution was filtrated, and the filtrate wasredissolved to 200 ml of a mixture of hexane and toluene in a weightratio of 1/1, and then thus obtained solution was filtrated, and theresultant filtrate was recrystallized to give a product.

[0342] The formula of the above-mentioned reaction steps is shown asfollows:

[0343] The ¹H-NMR spectrum of the obtained product is shown in FIG. 6.

[0344]¹H-NMR(CDCl₃) ppm: 0.7(t, 2H, CH₂), 1.2(t, 9H, OCH₂CH₃), 1.6(s,9H, t-Bu), 1.7(t, 2H, CH₂), 3.3(t, 2H, CH₂), 3.9(q, 6H, CH₂), 5.4(t, 1H,NH), 7.2(d, 4H, C₆H₄)

[0345] (iv) Modification of Silicasol

[0346] The compound synthesized in the step (iii) was mixed withcolloidal silica (manufactured by Nissan Chemical Industries, Ltd.,NPC-ST, silicasol content: 30% by weight) and 0.05 mol/L hydrochloricacid, in a weight ratio of the compound synthesized in the step(iii)/colloidal silica NPC-ST (without solvent)/hydrochloric acid being5/10/2.5 (modified amount of 50%) and 10/10/5 (modified amount of 100%),the mixture was stirred at room temperature for 16 hours to modifysilicasol (the former is mentioned as modified silicasol H, the latteris mentioned as modified silicasol I).

[0347] (3) Preparation of a Photosensitive Resin Composition

[0348] The photosensitive resin obtained in the step (1) and themodified silicasol obtained in the step (2) were mixed together in theratio specified in Table 8 (denoted by solid ratio without solvent) toprepare a photosensitive resin composition. Incidentally, the examplewithout the modified silicasol was made as Comparative Example 12.

[0349] 2. Pattern Formation and Evaluation of the Properties(Sensitivity, Resolution and Oxygen Plasma Resistance)

[0350] Conducted in the same way as Example 9. TABLE 8 CompositionModified Modified colloidal amount of Photosensitive silica colloidalresin (parts (parts by silica Sensitivity Resolution O₂-RIE rate byweight) weight) (%) (mJ/cm²) (μm) (nm/sec) Ex. 21 1 modified 50 12 0.142 silicasol H 0.43 Ex. 22 1 modified 100 22 0.14 9 silicasol I 0.25 Ex.23 1 modified 100 11 0.13 3 silicasol I 0.43 Comp. Ex. 1 0 — 32 0.22 8012

Example 24

[0351] (i) Synthesis of 1-(1-ethoxy)ethoxy-4-bromobenzene

[0352] Into 100 ml of dehydrated ethyl acetate, were fed 11.0 g (50mmol) of p-bromophenol, and 4.8 ml of a solution composed ofhydrochloric acid (1.0 mol/L) and ether, and the mixture was set at 40°C. Into the mixture, 10.8 g (150 mmol) of ethylvinylether was addeddropwise, and the mixture was kept with stirring for one night. Aftercompletion of the reaction, the reaction solution was rinsed with sodiumhydrogen carbonate solution and then rinsed with water to removesolvent. By purifying with silica gel column chromatography (eluate:hexane), 10.7 g (36.5 mmol) of 1-(1-ethoxy)ethoxy-4-bromobenzene wasobtained.

[0353] NMR(CDCl₃) ppm: 1.2(t, 3H, terminal CH₃), 1.49 (t, 3H, branchedCH₃), 3.47 to 3.6(m, 1H, OCH), 3.7 to 3.85(m, 1H, OCH), 5.34(q, 1H,branched OCH), 6.9(d, 2H, C₆H₄), 7.38(d, 2H, C₆H₄)

[0354] (ii) Synthesis of4-[2-{(3-trimethoxysilyl)propyloxycarbony}vinyl]-1-{(1-ethoxy)ethoxy}benzene

[0355] The objective compound was obtained in the same way with Hechreaction in the step (2) (ii) of Example 1, except for using1-(1-ethoxy)ethoxy-4-bromobenzene synthesized in the step (i) instead of1-(t-butoxycarbonyloxy)-4-iodobenzene in the step (2) (ii) in Example 1.

[0356] NMR(CDCl₃) ppm: 0.7(t, 2H, CH₂), 1.2(t, 3H, terminal CH₃),1.49(t, 3H, branched CH₃), 1.8(t, 2H, CH₂), 3.55 to 3.65(m, 9H, OCH₃),3.47 to 3.6(m, 1H, OCH), 3.7 to 3.85(m, 1H, OCH), 4.2(t, 2H, CH₂),5.34(q, 1H, branched OCH), 6.4(d, 1H, C=CH), 7.6(d, 1H, C=CH), 6.9(d,2H, C₆H₄), 7.38(d, 2H, C₆H₄)

Example 25

[0357] (i) Synthesis of 1-(1-ethoxy)ethoxy-4-bromobenzene

[0358] The objective compound was obtained in the same manner as thestep (i) in Example 24.

[0359] (ii) Synthesis of4-[2-(trimethoxysilyl)vinyl]-1-(1-ethoxy)ethoxybenzene

[0360] The objective compound was obtained in the same manner as Hechreaction in the step (2) (ii) of Example 1, except for using1-(1-ethoxy)ethoxy-4-bromobenzene and trimethoxyvinylsilane instead of1-(t-butoxycarbonyloxy)-4-iodobenzene and 3-trimethoxysilylpropylesterof acrylic acid.

[0361] NMR(CDCl₃) ppm: 1.2(t, 3H, terminal CH₃), 1.49(t, 3H, branchedCH₃), 3.47 to 3.6(m, 1H, OCH), 3.6(m, 9H, OCH₃), 3.7 to 3.85(m, 1H,OCH), 5.34(q, 1H, branched OCH), 6.1(d, 1H, C=CH), 7.18(d, 2H, C₆H₄),7.25(d, 1H, C=CH), 7.5(d, 2H, C₆H₄)

Example 26

[0362] (i) Synthesis of 1-benzyloxy-3-acetoxybenzene

[0363] Into 300 ml of dimethylsulfoxide, 30.4 g (200 mmol) ofresorcylmonoacetate was dissolved, and aqueous solution of sodiumhydrate (NaOH/H₂O: 8g/30 ml) was added to this solution and stirreduntil the mixture being uniform. Then, 26.5 g (210 mmol) of benzylchloride was added into the mixture, and allowed to react at roomtemperature for 24 hours. The reaction mixture was put into 1 L of icedwater, and the obtained solid was collected by filtration, dried andrecrystallized by ethanol to prepare 44.3 g (183 mmol) of1-benzyloxy-3-acetoxybenzene.

[0364] (ii) Synthesis of 3-benzyloxyphenol

[0365] In 300 ml of 10% water-containing ethanol, 20 g (82 mmol) of1-benzyloxy-3-acetoxybenzene obtained in the step (i) was hydrolyzedwith 16.3 g (248 mmol) of potassium hydroxide, and neutralized toprepare 14.8 g (74 mmol) of 3-benzyloxyphenol.

[0366] (iii) Synthesis of 1-(1-ethoxy)ethoxy-3-benzyloxybenzene

[0367] The objective compound was obtained in the same way with the step(i) of Example 24, except for using 3-benzyloxyphenol instead ofp-iodophenol.

[0368] (iv) Synthesis of 3-(1-ethoxy)ethoxyphenol

[0369] The objective compound was obtained in the same way with the step(2) (ii) of Example 21, except for using1-(1-ethoxy)ethoxy-3-benzyloxybenzene obtained in the step (iii) insteadof 1-benzyloxy-4-t-butoxycarbonyloxybenzene in the step (2) (ii) inExample 21.

[0370] (v) Synthesis of1-(1-ethoxy)ethoxy-3-[(3-triethoxysilyl)propylaminocarbonyloxy]benzene

[0371] The objective compound was obtained in the same way with the step(2) (iii) of Example 21, except for using 3-(1-ethoxy)ethoxyphenolobtained in the step (iv) instead of 4-t-butoxycarbonyloxyphenol.

[0372] The formula of the above-mentioned reaction steps is shown asfollows:

Example 27

[0373] (i) Synthesis of 1-benzyloxy-3-t-butoxycarbonyloxybenzene

[0374] The objective compound was obtained in the same way with the step(2) (i) of Example 21, except for using 3-benzyloxyphenol instead of4-benzyloxyphenol in the step (2) (i) in Example 21.

[0375] (ii) Synthesis of 3-t-butoxycarbonyloxyphenol

[0376] The objective compound was obtained in the same way with the step(2) (ii) of Example 21, except for using1-benzyloxy-3-t-butoxycarbonyloxybenzene obtained in the step (i)instead of 1-benzyloxy-4-t-butoxycarbonyloxybenzene in the step (2) (ii)in Example 21.

[0377] (iii) Reaction of 3-t-butoxycarbonyloxyphenol with SilaneCoupling Agent

[0378]1-[3-(Trimethoxysilyl)propylaminocarbonyloxy]-3-[t-butoxycarbonyloxy]benzenewas obtained in the same way with the step (2) (iii) of Example 21,except for using 3-t-butoxycarbonyloxyphenol obtained in the step (ii)instead of 4-t-butoxycarbonyloxyphenol in the step (2) (iii) in Example21.

[0379] The formula of the above-mentioned reaction steps is shown asfollows:

Example 28 Synthesis of 2-(triethoxysilyl)-1-(t-butoxycarbonyl)ethane

[0380] Into the 100 ml of dried tetrahydrofuran, were fed 25.8 g (20mmol) of t-butyl acrylate and 32.8 g (20 mmol) of triethoxysilane, andthe mixture was substituted by argon. To the mixture solution, 10 mg ofchloroplatinic acid was added and the mixture was heated for 24 hoursunder reflux. After completion of the reaction, 58.5 g of the objectivecompound was obtained by removing solvent.

Example 29 Synthesis ofN-[2-(t-butoxycarbonyl)ethyl]-3-(triethoxysilyl)propylamine

[0381] In dehydrated ethanol, 22.1 g (100 mmol) of3-aminopropyltriethoxysilane was dissolved, and to the solution, wasadded 12.8 g (100 mmol) of t-butyl acrylate, and the mixture was stirredat room temperature for 24 hours. After completion of the reaction, 32.5g of the objective compound was obtained by removing solvent.

[0382] NMR(CDCl₃) ppm: 0.6(t, 2H, CH₂), 1.19(t, 9H, CH₃), 1.41(s, 9H,t-Bu), 1.49 to 1.67(m, 2H, CH₂), 2.4(t, 2H, CH₂), 2.59(t, 2H, CH₂),2.8(t, 2H, CH₂), 3.79(q, 6H, OCH₂)

[0383] The above-mentioned reaction formula is shown as follows:

Example 30 Synthesis ofN,N′-di-(t-butoxycarbonyl)ethyl-3-(triethoxysilyl)propylamine

[0384] The objective compound was obtained in the same way with Example29, except for using 25.6 g (200 mmol) of t-butylester of acrylic acidand heating for 24 hours under reflux.

[0385] NMR(CDCl₃) ppm: 0.5(t, 2H, CH₂), 1.19(t, 9H, CH₃), 1.39(s, 18H,t-Bu), 1.41to 1.6(m, 2H, CH₂), 2.3(t, 6H, CH₂), 2.7(t, 4H, CH₂), 3.75(q,6H, OCH₂)

[0386] The above-mentioned reaction formula is shown as follows:

[0387] Then, the properties of pattern were evaluated in the same manneras Example 2, except for using the compounds (active components)obtained in Examples 24 to 30 instead of the active component used inExample 2. The results of Examples 24 to 30 were same as the results ofExample 2.

1. An active component for using in combination with a photosensitizerwhich constitutes a photosensitive resin composition, wherein thecomponent comprises at least one member selected from the groupconsisting of an active metal alkoxide represented by the followingformula (1): (X)_(m−n)-M^(m)-[(U₁)_(p)-(U₂-Z)_(t)]_(n)  (1) wherein, Xrepresents a hydrogen atom, a halogen atom, an alkoxy group or analkoxycarbonyl group, M represents a metal atom whose valence m is notless than 2, U₁ represents a first connecting unit, U₂ represents asecond connecting unit, Z represents a group causing a difference insolubility by light exposure, n represents an integer of not less than 1and m>n, p represents 0 or 1, and t represents an integer of not lessthan 1, or a polycondensate thereof, and a particle represented by thefollowing formula (2): P—[(Y)_(s)-{(U₁)_(p)-(U₂-Z)_(t)}]_(k)  (2)wherein, P represents a fine particle carrier, Y represents a couplingresidue, k represents an integer of not less than 1, s represents 0 or1, and U₁, U₂, Z, p and t have the same meanings defined above.
 2. Anactive component according to claim 1, which is in the form of aparticle, or an oligomer.
 3. An active component according to claim 1,wherein the group Z is (a) a photo-crosslinkable group or aphoto-curable group, or (b) a hydrophilic group protected by aprotective group which is capable of removing by light exposure.
 4. Anactive component according to claim 1, wherein the group Z is ahydrophilic group protected by a protective group which is capable ofremoving by light exposure in association with a photosensitizer.
 5. Anactive component according to claim 3, wherein the protective group iscapable of removing by an acid.
 6. An active component according toclaim 1, wherein the group Z is capable of forming a hydroxyl group or acarboxyl group by removal of a hydrophobic protective group.
 7. Anactive component according to claim 3, wherein the protective group is(i) a protective group for a hydroxyl group, selected from the groupconsisting of an alkoxyalkyl group, an acyl group, an alkoxycarbonylgroup, an oxacycloalkyl group and a crosslinked cyclic alicyclic group;or (ii) a protective group for a carboxyl group, selected from the groupconsisting of an alkyl group, a carbamoyl group and a crosslinked cyclicalicyclic group.
 8. An active component according to claim 3, whereinthe protective group is (1) a protective group for a hydroxyl group,selected from the group consisting of a C₁₋₆alkyl-carbonyl group, aC₁₋₆alkoxy-C₁₋₆alkyl group, a C₁₋₆alkoxy-carbonyl group and anoxacycloalkyl group; or (2) a protective group for a carboxyl group,selected from the group consisting of a C₁₋₆alkyl group, a carbamoylgroup, a C₁₋₆alkyl-carbamoyl group, a C₆₋₁₀aryl-carbamoyl group and abi- or tricycloalkyl group.
 9. An active component according to claim 1,wherein the metal atom M is one member selected from the groupconsisting of aluminium, titanium, zirconium and silicon.
 10. An activecomponent according to claim 1, wherein the metal atom M is silicon. 11.An active component according to claim 1, wherein each of the connectingunits, U₁ and U₂, is a unit containing at least one member selected fromthe group consisting of a chain hydrocarbon, a hydrocarbon ring, a chainhydrocarbon having a hetero atom, and a heterocycle.
 12. An activecomponent according to claim 1, wherein the connecting units U₁ and U₂are respectively represented by the following formulae:—(R¹)_(q)—(B)_(r)—, —(R²)_(u)—(Ar)_(v)—wherein, each of the factors, R¹and R² is either same or different, representing an alkylene group or analkenylene group, B represents an ester bond, a thioester bond, an amidebond, a urea bond, a urethane bond, a thiourethane bond, an imino group,a sulfur atom or a nitrogen atom, Ar represents an arylene group or acycloalkylene group, each of the factors, q, r, u and v, represents 0 or1, and q+r+u+v≧1.
 13. An active component according to claim 1, wherein,in the formula (1), Z means a hydroxyl or carboxyl group protected by ahydrophobic protective group which is capable of removing by lightexposure, the metal atom M is selected from the group consisting ofaluminium, titanium, zirconium and silicon, and the unit(U₁)_(p)-(U₂-Z)_(t) containing a connecting unit is represented by thefollowing formula: [(R¹)_(q)—(B)_(r)]_(p)—[{(R²)_(u)—(Ar)_(v)}-Z]_(t)wherein, R¹, R², B, Ar, p, q, r, t, u and v have the same meaningsdefined above.
 14. An active component according to claim 1, wherein thepolycondensate is a polycondensate of the active metal alkoxiderepresented by the formula (1) and a metal alkoxide represented by thefollowing formula (5): (X)_(m−n−1)M^(m)(R⁵)_(n−1)  (5) wherein, R⁵represents a hydrogen atom or an alkyl group, X, M, m and n have thesame meanings defined above.
 15. An active component according to claim14, the weight ratio of the active metal alkoxide (1) relative to themetal alkoxide (5) is 10/90 to 90/10.
 16. An active component accordingto claim 1, wherein the polycondensate is in the form of a particlehaving a mean particle size of 1 to 100 nm.
 17. An active componentaccording to claim 1, wherein the mean particle size of the fineparticle carrier is 1 to 100 nm.
 18. An active component according toclaim 1, wherein the fine particle carrier comprises an inorganic fineparticle carrier.
 19. An active component according to claim 1, whereinthe fine particle carrier comprises a silicasol.
 20. An active componentaccording to claim 1, which comprises a connecting unit U connectingwith an inorganic fine particle P whose mean particle size is 1 to 50 nmthrough a silane coupling agent Y, a hydrophilic group connecting withthe connecting unit, and a protective group which protects thehydrophilic group, wherein the hydrophilic group and the protectivegroup constitute a group Z which causes a difference in solubility bylight exposure; the connecting unit comprises at least one memberselected from the group consisting an aromatic C₆₋₁₂hydrocarbon ring, amonocyclic alicyclic hydrocarbon ring, a crosslinked cyclic alicyclichydrocarbon ring and an aliphatic hydrocarbon chain; the hydrophilicgroup is a hydroxyl group or a carboxyl group; and the protective groupis (1) a protective group for the hydroxyl group, selected from thegroup consisting of a C₁₋₄alkyl-carbonyl group, a C₁₋₄alkoxy-C₁₋₄alkylgroup, a C₁₋₄alkoxy-carbonyl group and a 5- or 6-membered oxacycloalkylgroup, or (2) a protective group for the carboxyl group, selected fromthe group consisting of a C₁₋₄alkyl group, a carbamoyl group, aC₁₋₄alkyl-carbamoyl group, a C₆₋₁₀aryl-carbamoyl group and a bi- ortricycloalkyl group.
 21. An active component according to claim 20,wherein the amount of the silane coupling agent is 0.1 to 200 parts byweight relative to 100 parts by weight of the fine particle carrier. 22.A photosensitive resin composition which comprises a base resin, aphotosensitizer and an active component recited in claim
 1. 23. Aphotosensitive resin composition according to claim 22, which is apositive one in which an exposed area is water- or alkali-soluble.
 24. Aphotosensitive resin composition according to claim 22, wherein the baseresin comprises a homo- or copolymer of a monomer which is capable offorming a hydrophilic group by an action of an acid, and thephotosensitizer comprises an photoactive acid generator.
 25. A processfor forming a pattern, which comprises applying or coating aphotosensitive composition recited in claim 22 onto a substrate,exposing the coating layer to light, heat-treating the light-exposedlayer, and developing the heat-treated layer to form a pattern.
 26. Anactive metal alkoxide which is represented by the following formula (1):(X)_(m−n)-M^(m)-[(U₁)_(p)-(U₂-Z)_(t)]_(n)  (1) wherein, X represents ahydrogen atom, a halogen atom, an alkoxy group or an alkoxycarbonylgroup, M represents a metal atom whose valence m is not less than 2, U₁represents a first connecting unit, U₂ represents a second connectingunit, Z represents a group causing a difference in solubility by lightexposure, n represents an integer of not less than 1 and m>n, prepresents 0 or 1, and t represents 1 or
 2. 27. An oligomer or an activeparticle, which comprises at least a polycondensate of an active metalalkoxide recited in claim 26.